Use of SPMD Technology for a Probabilistic Assessment - USGS

USE OF SEMIPERMEABLE MEMBRANE DEVICE (SPMD)

TECHNOLOGY FOR A PROBABILISTIC ASSESSMENT

OF HYDROPHOBIC ORGANIC CONTAMINANTS IN

SELECTED REACHES OF VIRGINIA RIVERS

By:

W.L. Cranor D.A. Alvarez S. D. Perkins

G.A. Tegerdine R.C. Clark

J.N. Huckins

U.S. Geological Survey/Columbia Environmental Research Center

4200 New Haven Road

Columbia, MO 65201

Prepared For:

Mr. Roger E. Stewart

Virginia Department of Environmental Quality

Office of Water Quality Assessment and Planning

629 East Main Street Richmond, Virginia 23219

June 10, 2005

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EXECUTIVE SUMMARY

This report summarizes findings from a probabilistic monitoring program using lipid-

containing semipermeable membrane devices (SPMDs) to monitor trace to ultra-trace levels

of toxic hydrophobic organic contaminants for the further characterization of water quality at

the small watershed level within the Commonwealth of Virginia. SPMDs were chosen for

this study because of their ability to passively extract large volumes of water over extended

exposure periods (i.e., one month or more), which permits the detection or quantitation of

very-low levels of toxic organic compounds in aquatic systems. The work was conducted as

part of a collaborative effort between the U.S. Geological Survey’s (USGS) Columbia

Environmental Research Center (CERC) and the Virginia Department of Environmental

Quality (VDEQ). The study was designed to satisfy the Code of Virginia, § 62.1-44.19:5,

Water Quality and Reporting requirements, which include expanding the percentage of river

and stream miles monitored and providing information about trace levels of toxic organic

compounds in riverine water columns. These efforts will aid in the assessment of the quality

of free flowing freshwater streams in Virginia.

Fifty sites, representing Virginia’s freshwater streams, were selected for this study based on

probabilistic modeling by the VDEQ. The SPMDs were fabricated by CERC scientists and

replicate samplers were deployed by VDEQ personnel at all 50 sites. After the exposure

phase, SPMDs were shipped to CERC for analysis. SPMDs were recovered from 46 of the 50

sites. These samples were processed and analyzed for several classes of chemicals, which

include polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs),

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organochlorine pesticides (OCPs), and selected “current use” pesticides including trifluralin,

diazinon, dacthal, chlorpyrifos, endosulfans, and permethrins (see Table 1 for complete list of

targeted contaminants). Previously developed models were employed to estimate water

concentrations of contaminants of concern in the water columns of the rivers studied.

Residue levels of several OCPs and PAHs in SPMDs were found above the method detection

limit (MDL; see “Limits of Detection and Quantitation” section for a definition) at all sites.

However, only the concentrations of the OCP pentachloroanisole (PCA) were at or above the

method quantitation limit (MQL; see “Limits of Detection and Quantitation” section for a

definition) in SPMDs from every site analyzed. Although PCA is classified as an OCP, it is a

microbial methylation product of the wood-preservative pentachlorophenol and a metabolite

of pentachloronitrobenzene (a fungicide used for potatoes) in fish tissues. A number of the

sites had quantifiable levels (≥ MQL) of some of the other OCPs in SPMDs, which include

the chlordanes, the nonachlors, hexachlorobenzene (HCB), dieldrin and endrin. At one site

(ID 9-SNK019.59), concentrations of methoxychlor in SPMDs were significantly higher (i.e.,

eight-fold) than levels found in SPMDs from the next highest site. The highest concentrations

of individual PAHs in SPMDs were phenanthrene, fluoranthene and pyrene, which are three

of the sixteen PAHs listed by the U.S. Environmental Protection Agency as priority

pollutants. This finding is characteristic of the pattern of PAHs emitted from pyrogenic

sources. Fluoranthene was present in SPMDs at detectable levels at every site. In several

SPMD samples, methylated PAHs were also observed, which are characteristic of the pattern

of PAHs emitted from petrogenic sources. More than half of the study sites also had

detectable levels of at least one of the current-use pesticides. Endosulfans were the most

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ubiquitous of the current-use pesticides, with detectable levels found at 33 of the 46 sites

sampled. All of the pesticides classified as current-use were detected (≥ MDL), when

considering the concentrations of pesticides across the 46 sites. Concentrations of PCBs in

SPMDs were above the MDL at only two sites and the level at only one site was above the

MQL.

Water concentrations reported in this study were derived from SPMD levels using published

calibration data and an Excel-based water concentration calculator. These estimates were

made for all SPMD concentration data above the MDLs with no censoring of values that fail

to meet the MQLs. Also, concentrations were not adjusted for the number of significant

figures. Note that the analytical limitations of this work justify, at most, two significant

figures. For reported values of SPMD concentrations, this constraint is solely due to

cumulative errors or variability associated with processing, cleanup and analysis of

environmental samples. In the case of estimated water concentrations, additional variability

is introduced by the extrapolation of ambient water concentrations from SPMD

concentrations. Based on earlier work, a maximum of about a two-fold difference between

SPMD derived water concentrations and independently measured values would be expected.

Examination of contaminant concentrations in SPMDs and in water show that relatively low

concentrations of an analyte in an SPMD can extrapolate to a relatively high concentration of

the same analyte in the exposure water. For example, estimates of the concentrations of

diazinon were generally among the highest of the toxic chemicals detected in the water

column, but diazinon concentrations in SPMDs consistently fell between the MDL and the

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MQL. The reason that low concentrations of diazinon in SPMDs translate into relatively high

concentrations in the water column is that diazinon has a relatively low SPMD-water

partition coefficient (< 103), and thus the volume of water extracted by the SPMD is

relatively low. Conversely, a relatively high SPMD concentration of an analyte with a high

SPMD-water partition coefficient (> 104) can extrapolate to a relatively low concentration of

the same compound in the exposure water.

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TABLE OF CONTENTS

EXECUTIVE SUMMARY……………………………………………………………….2

TABLE OF CONTENTS ……………………………………………………………….6

INTRODUCTION …………………………………………………………………….7

EXPERIMENTAL …………………………………………………………………….10

RESULTS AND DISCUSSIONS ………………………………………..……………...28

ACKNOWLEDGEMENTS……………………………………..………………………..33

LITERATURE CITED…..……………………………………….…………………….. 34

TABLES …………………………………………………...………………………….. 36

FIGURES ……………………………………………………………………...………..134

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INTRODUCTION

During the last century, rivers within the Commonwealth of Virginia have experienced a

decline in indices of aquatic ecological health. The Virginia Department of Environmental

Quality (VDEQ) has been charged, through The Code of Virginia, § 62.1-44.19:5 Water

Quality and Reporting Regulations, with monitoring those factors which may be indicators of

water quality in both free flowing freshwater streams and in estuarine waters. The VDEQ has

adopted a water quality monitoring strategy which incorporates a probabilistic monitoring

program for free flowing freshwater streams, consisting of all non-tidal perennial streams and

rivers within the Commonwealth of Virginia. The main objective of this program is to

determine what proportion of the state’s streams is fully, partially, or not supporting fishing,

swimming, and aquatic life. The focus of this work is the assessment of benthic macro-

invertebrate populations, standard water quality chemistry, metals and toxic organic

contaminants in sediments, and dissolved organics in the water column.

As an integral part of this much larger study, lipid-containing semipermeable membrane

devices (SPMDs) were used to sample the hydrophobic-organic contaminants in the water

columns of selected streams. Extracts of exposed SPMDs were analyzed to determine ultra-

trace (i.e., < ng/L) and trace (ng/L to mg/L) concentrations of polycyclic aromatic

hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs),

and selected current-use pesticides including trifluralin, diazinon, dacthal, chlorpyrifos,

endosulfans, and permethrins (see Table 1 for a complete list of targeted contaminants) in

stream waters.

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Prior to the advent of SPMD technology, ultra-trace levels of many contaminants in water

were often below the detection limits of most commonly employed low volume (i.e., ≤ 5 L)

sampling methods. Also, the probabilities of detecting chemicals from episodic discharge

events were very low, because sampling with conventional methods only provides

concentration data on a single point in time. To address these types of sampling and

analytical methods issues, scientists at the USGS’s CERC developed the SPMD for in situ

passive monitoring of aquatic contaminants (1-5). These devices have been standardized (5)

and are commercially available.

In theory, lipid containing SPMDs are well suited for all neutral organic compounds with log

octanol-water partition coefficients (Kows) ≥ 3.0, which include the contaminants targeted for

this project and generally all persistent organic pollutants (POPs). Sampling of hydrophobic

organic compounds with log Kows >5.0 will generally remain integrative (i.e., no significant

losses of residues accumulated in the device, even when ambient concentrations fall)

throughout a 30 day (d) exposure period. A 1-mL triolein “standard SPMD” will passively

extract hydrophobic contaminant residues from about 1 to 10 L of water per day (5).

Therefore, hydrophobic contaminants may be extracted from more than 100 L of water by a

single 1-mL triolein SPMD during a 30 d exposure period. When sampling is integrative and

uptake is linear, residue concentrations in SPMDs represent time weighted average (TWA)

concentrations of exposure water. However, sampling is often not integrative throughout a 30

d exposure period when the log Kows of compounds of interest are between 3.0 and 5.0.

When performance reference compounds (PRCs; see description below) are used in SPMDs

(6), ambient water concentrations can be determined even when SPMD concentrations

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approach equilibrium, i.e., residue uptake is curvilinear. However, the reduced amount of

chemical accumulated by an SPMD during the curvilinear phase of uptake is no longer

representative of integrative sampling.

Differences in exposure conditions such as turbulence/flow rate, biofouling and temperature

affect SPMD sampling rates. Depending on the design of the deployment apparatus used to

protect SPMDs, the effects of environmental conditions on a chemical’s sampling rate can be

as great as an order of magnitude. Thus, site-specific in situ SPMD sampling rates are needed

to determine ambient concentrations of chemicals from their respective levels in SPMDs.

The use of PRCs as described by Huckins et al. (6) permits the estimation of in situ sampling

rates. PRCs are compounds added to SPMD lipid prior to deployment, which have moderate

to relatively high release rates over the course of a sampling period and do not interfere with

the analysis of the chemicals targeted in a study. Generally, a mixture of PRCs with a range

of Kows is used for environmental SPMD exposures (see “PRC Identification and Use”

section for further information). Huckins et al. (6) have shown that the in situ rate of loss of

PRCs can be used to adjust laboratory calibration data of the chemicals of concern to site-

specific field conditions (5, 6). Fortunately, equations and a large set of SPMD calibration

data are available for the derivation of the aqueous concentrations of most of the

contaminants detected in this study. Furthermore, two different studies have shown that

estimates of ambient water concentrations derived from SPMD concentrations are generally

within two fold of the average concentrations of the same chemicals measured throughout the

exposure period using a liquid-liquid extraction reference method (5, 6, 7).

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EXPERIMENTAL

Materials and Reagents

Analytical standards of all targeted chemicals (Table I), were obtained from AccuStandard

Inc., New Haven, CT, ChemService Inc., West Chester, PA, Crescent Chemical, Islandia,

NY, or Sigma Aldrich, St. Louis, MO. All laboratory chemicals were American Chemical

Society (ACS) reagent grade and organic solvents were Optima grade from Fisher Scientific

Co., Pittsburgh, PA. Florisil (60-100 mesh) was obtained from Fisher Scientific Company,

Pittsburgh, PA. The Florisil was heated at 475 oC for 8 hours, blended with 5 % (w/w) of

deionized water, equilibrated at 130 oC for 48 hours, and stored at room temperature in a

desicator with P2O5 as a desiccant. Silica gel (SG-60, 70-230 mesh) was obtained from

Thomas Scientific, Swedesboro, NJ. The silica gel (SG) was washed with 40:60 (V/V)

methyl t-butyl ether (MTBE): hexane followed by 100% hexane, then, after solvent removal,

activated at 130 oC for 72 hours before use. The SG was with P2O5 as a desiccant.

Phosphoric acid/SG (PASG) was made by combining hexane washed phosphoric acid and

the aforementioned SG in a 40:60 (w/w) ratio. The PASG was blended to achieve

homogeneity, and subsequently with P2O5 as a desiccant. Potassium silicate (KS) was made

by combining a methanolic solution of potassium hydroxide (KOH) with the SG. The

methanol/KOH ratio used was 250 mL of methanol to 56 grams of potassium hydroxide

(KOH/CH3OH, 28/72, w/w), which was mixed with 100 grams of SG. After mixing for 1.5

hours at 55 oC and solvent removal, the KS was activated at 130 oC for 48 hours before use

and subsequently stored at room temperature in a dessicator with P2O5 as a desiccant.

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Low density polyethylene (LDPE) layflat tubing was purchased from Environmental

Sampling Technologies, St. Joseph, MO. The tubing was a 2.54 cm wide, No. 940, untreated

(pure PE; no slip additives, antioxidants, etc.) clear tubing. The wall thickness of this lot

ranged from 84 to 89 µm. Triolein (1,2,3-tri-[cis-9-octadecenoyl]glycerol) was obtained from

Nu-Check Prep Inc., Elysian, MN. Although the purity of triolein was certified as ≥ 99%

(Lot T-235-05-L), it was further purified by the method of Lebo et al. (8) prior to use in the

preparation of SPMDs.

SPMD Preparation

All of the SPMDs used in this project consisted of 109.2-cm long by 2.5-cm wide layflat

LDPE tubing (cleaned up as described by Huckins et al. [5]) containing 1.0 mL of purified

triolein. The SA/V (membrane surface area to total SPMD volume) ratio of SPMDs used in

this study was ≈ 86-cm2/mL and triolein represented ≈ 20% of the mass of the SPMDs. The

average weight of individual SPMDs was 4.5 g with a range of 4.4 to 4.6 g. This variation in

SPMD mass was due to slight differences in the thickness of the LDPE membrane. These

specifications conform to a “standard SPMD” as defined by Huckins et al. (5).

PRC Selection and Use

Four of the five SPMDs deployed at each site were spiked with 14 µg of each of the five

perdeuterated PRCs (note: one SPMD from each site was kept in reserve for potential

biomarker assessment). Also, one of the two field-blank SPMDs was similarly spiked with

PRCs, while the remaining SPMD was reserved for use as a biomarker blank. Ideally, the

amount of PRC residues lost during an exposure should fall between about 50 % and 80 %

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(5). However, > 80 % losses of PRCs are acceptable as long as remaining concentrations are

greater than its MQL.

Identification of Sampling Sites

Table II gives a description of CERC site number identification with cross reference to

VDEQ station ID name. Additional information on site locations and characteristics is

available from the VDEQ.

Sample Definition

In this study, an SPMD sample is defined as a composite of two-standard 1-mL triolein

SPMDs. Thus, each site was represented by two replicate samples and one SPMD kept in

reserve.

Sample Transport, Storage, Deployment and Retrieval

After preparation and spiking selected SPMDs with PRCs, the SPMDs were transferred to

solvent-rinsed gas tight metal cans. Note: SPMDs with and without PRCs were stored in

separate cans. The cans were immediately flushed with argon and sealed for storage. All cans

with SPMDs were stored in a freezer at < 15 °C until shipping to VDEQ. When notified by

the VDEQ, canned SPMDs were shipped overnight in coolers to Virginia. At each sample

site, personnel from various regions of the VDEQ mounted five SPMDs into a specially

prepared protective cage. Two additional SPMDs were used for field blanks at each sample

site. After SPMD deployment, cans were resealed and stored by VDEQ personal at various

locations.

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Exposure periods and temperatures varied across sampling sites and deployments as shown

in Table III. VDEQ personnel recorded site locations, average water temperatures, and the

dates and times of deployment and retrieval. After exposures, SPMDs were recovered and

sealed in the same cans as used for shipping to the field. Some cans were stored at VDEQ

facilities in freezers at < 15 °C for short periods of time, while others were stored similarly

for several months before shipping back to CERC. However, sample storage by the VDEQ

did not exceed six months and an earlier report (5) indicated that losses of relatively volatile

2,4,5-trichlorophenol from frozen SPMDs (< −15 °C) did not occur after six months storage

in a freezer. Finally, all SPMDs were shipped in their cans overnight in coolers on ice to

CERC.

CERC Storage and Custody

Following receipt of the SPMDs at CERC and prior to processing, the SPMDs were stored in

a laboratory freezer at < −15 °C until processing and analysis. Again, sample storage times

varied but were less than six months.

Overview of Processing, Cleanup, and Fractionation of Samples

The procedures used for preparing samples for analysis in this study are similar to published

approaches (5). Also, specific details have been previously reported to VDEQ with a high

degree of detail (9). The general sample processing and enrichment scheme is shown in

Figure 1 and is summarized sequentially below:

1) SPMD Membrane Cleaning

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2) SPMD Dialysis (i.e., Recovery of Analytes)

3) Dialysis Sample Splitting

4) Size Exclusion Chromatography (SEC)

5) Class Specific Fractionation/Cleanup

Herein, we provide brief descriptions of these processing, cleanup and fractionation

procedures.

Cleaning of the Exterior Membrane Surface: The following procedures were developed to

remove any contaminant residues present in periphyton growths on the exterior of the LDPE

membrane surface and to ensure adequate dialytic recovery of all analytes with high Kows

(log Kow ≥ 6.0). SPMDs (n = 2) representative of a sample (includes field blanks) were

placed in a glass beaker with about 200 mL of hexane and were agitated for about 20 to 30

seconds before discarding the hexane. Subsequently, sample SPMDs were placed in a

stainless steel pan and thoroughly washed with clean running water, while being scrubbed

vigorously with a clean toothbrush. At this point the SPMDs were examined for holes in the

membrane and none were found (note: any holes found would have been isolated by heat

sealing). After the integrity of the SPMDs was ensured, the SPMDs were submerged in a

tank of 1-M HCl for approximately 30 seconds to remove any remaining adhering mineral

salts. Following the HCl treatment, the SPMDs were again rinsed with running water to

remove the acid. All water on the membrane surface was removed by rinses of acetone,

followed by isopropanol. The SPMDs were allowed to air dry for a minimal time period

(typically < 6 minutes) on a piece of solvent rinsed aluminum foil.

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Dialytic Recovery of Analytes: After surficial cleaning, each SPMD was dialyzed for 18

hours by submersion in ≈ 165 mL of hexane in a glass jar (i.e., a dialysis chamber equipped

with a foil lined lid) maintained at 18 oC. The hexane was removed and transferred into an

evaporation flask. Then, a second volume of ≈ 165 mL of hexane was added to each dialysis

chamber and the SPMD was dialyzed for an additional 8 hours at 18 oC. The first and second

dialysates were combined in the evaporation flask and the SPMD was discarded. The

combined dialysates were reduced to a volume of 3-5 mL with a rotoevaporation system, and

quantitatively transferred through a pre-rinsed glass fiber filter into appropriately labeled

graduated test tubes. The solvent volume was then adjusted to 10.0 mL.

Sample Splitting: Because different enrichment techniques were required for the targeted

environmental contaminants, each sample was split into two equal portions (equivalent to

one SPMD) prior to further fractionation and enrichment. These were identified as the

“PAH” fractions and the “OCP/PCB” fractions. After splitting, the two fractions were each

reduced to a volume of ≈ 1 mL using high purity N2 blow down.

SEC Cleanup: A Perkin-Elmer Series 410 high performance liquid chromatograph (HPLC)

from Perkin-Elmer, Inc., Norwalk, CT, was employed as the solvent delivery system for

SEC. The SEC column was a 300-mm x 21.2-mm I.D. (10-µm particle size, 100 Å pore size)

Phenogel column (Phenomenex, Inc., Torrance, CA), equipped with a 50-mm x 7.5-mm I.D.

Phenogel guard column. A DFW-20 series fixed wavelength UV absorption detector (D-Star

Instruments, Inc. Manasses, VA) operating at 254 nm, a Hewlett-Packard Co, HP 3396 Series

II Integrator (Hewlett Packard, Inc., Palo Alto, CA), and an ISCO Foxy 200 (ISCO, Inc.,

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Lincoln, NE) fraction collector completes the SEC system. The SEC cleanup was

accomplished using a “collect window” defined by daily calibration. For the “PAH”

fractions, the collect window was initiated at the point of 70% of the time between the apexes

of the di(2-ethylhexyl) phthalate (DEHP) and the biphenyl chromatographic peaks. For the

OCP/PCB fractions, the collect window was initiated at the point of 50% of the time between

the apexes of the DEHP and the biphenyl chromatographic peaks. In both cases, the collect

windows were terminated at 70% of the time between the apexes of the coronene and the

sulfur chromatographic peaks. All collected fractions from the SEC system were amended

with ≈ 2 mL of isooctane, reduced to a volume of ≈ 1 mL on a rotoevaporation system, and

quantitatively transferred with hexane into appropriately labeled test tubes.

Further Cleanup-PAHs: The SEC-PAH fractions were treated with a tri-adsorbent column

consisting of (from top to bottom): 3-g PASG, 3 g of KS, and 3 g of SG. The tri-adsorbent

column was eluted with 50 mL of 4% MTBE:hexane (V/V). This procedure resulted in a

solution suitable for the instrumental analysis of PAH residues. The collected fractions were

amended with ≈ 2 mL of isooctane, reduced to a volume of ≈ 0.5 mL on a rotoevaporation

system, and quantitatively transferred with hexane into labeled 2 mL gas chromatography

(GC) autosampler vials. Following addition of an appropriate amount of the instrumental

internal standard (IIS), sample volumes were adjusted to 1.0 mL for GC-mass specific

detector (MSD) analysis.

Further Cleanup and Class Fractionation-OCPs/PCBs: The SEC-OCP/PCB fractions were

further enriched using column chromatography. Each fraction (1.0 mL of hexane) was

applied to a Florisil (5 g) column and eluted with 60 mL of 75:25 (V/V) MTBE:hexane. The

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column eluates were each amended with 5 mL of isooctane, and reduced in volume to ≈ 0.5

mL. These ≈ 0.5-mL samples were applied to SG columns (5 g) for class fractionation. Two

fractions were eluted from each SG column. The first fraction (SG1; 46 mL of hexane)

contains > 95 % of the total PCBs, hexachlorobenzene (HCB), heptachlor, mirex and ≈ 40 to

80 % of the p,p’-DDE when present in extracts. The second fraction (SG2; 75 mL of 40:60

[V/V] MTBE:hexane) contains the remaining 28 OCPs given in Table 1 and ≤ 5 % of the

total PCBs (largely, mono- and dichlorobiphenyl congeners). The SG1 and SG2 fractions

were each reduced to a volume of ≈ 0.5 mL and quantitatively transferred with hexane into

labeled GC vials. Samples were amended with appropriate IIS and the volumes were adjusted

to 1.0 mL using hexane and high purity N2 blow-down. These samples, identified as SG1 and

SG2, were then ready for GC-electron capture detector (ECD) analysis for PCBs and OCPs.

Instrumental Analysis-PAHs and PRCs

Gas chromatographic analyses for selected PAHs and PRCs were conducted using an Agilent

6890 GC equipped with an Agilent 7683 autosampler (Agilent Technologies, Inc.,

Wilmington, DE). One μL of each sample extract (1-mL volume) was injected using the

“cool-on-column” technique with helium as the carrier gas. An HP-5MS (30 m x 0.25 mm

i.d. x 0.25 μm film thickness) capillary column (Agilent Technologies, Inc., Wilmington,

DE) was used with the following temperature program: samples were injected at 50 °C, held

for 2 min, ramped at 25 °C/min to 130 °C, held for 1 min, then 6 °C/min ramp to 310 °C and

held at 310 °C for 5 min. Analytes were detected with a 5973 MSD (Agilent Technologies,

Inc., Palo Alto, CA) in the selected ion mode (SIM). Detector zone temperatures were set at

310 °C for the MSD transfer line, 150 °C at the quadrupole, and 230 °C at the source.

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Quantitation of the analytes was accomplished using a six-point curve with internal

calibration. Concentrations of calibration standards bracketed the range of 0.02 to 4.0µg/mL

for each of the analytes with the internal standards 2-methylnaphthalene-d10 and

benzo[e]pyrene-d12 maintained at 0.250 µg/mL.

Instrumental Analysis-PCBs and OCPs

Gas chromatographic analyses for PCBs and OCPs were conducted using a Hewlett Packard

5890 series gas chromatograph (GC) equipped with a Hewlett Packard 7673A autosampler

(Hewlett Packard, Inc., Palo Alto, CA). One μL of each sample extract (1-mL volume) was

injected using the "cool-on-column" technique with hydrogen as the carrier gas. Analyses of

SG-1 and SG-2 fractions for PCBs and OCPs were performed using a DB-35MS (30 m x

0.25 mm i.d. x 0.25 µm film thickness) capillary column (J&W Scientific, Folsom, CA) with

the following temperature program: injection at 90 oC; 15 oC/min to 165 oC; followed by 2.5

oC/min to 250 oC; then 10 oC/min to 320 oC. The electron capture detector (ECD, Hewlett

Packard, Inc., Palo Alto, CA) was maintained at 330 oC. Quantitation of OCPs in SG-1 and

in SG-2 samples was accomplished using a six-point internal standard calibration curve with

PCB congener I-30 as retention time reference compound and PCB congener I-207 as the

IIS. The concentrations of the pesticide standards ranged from 1.0- to 80-ng/mL.

Quantitation of total PCBs in the SG-1 fractions was accomplished using a six point internal

standard calibration curve employing standard solutions containing a 1:1:1:1 mixture of

Aroclors 1242, 1248, 1254, and 1260 with PCB congener I-30 as retention time reference

compound and PCB congener I-207 as the IIS. The levels of the total PCB standards ranged

from 200-to 4,000-ng/mL. The SG-2 fractions were not included in the analysis for total

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PCBs. Carry-over of mono- and dichlorobiphenyl congeners into the SG-2 fraction

represents, at most, an additional 5% of total PCBs. The more rigorous approach of analysis

of the SG-2 fraction for these few PCB congeners was beyond the scope of the project and

was judged to be an excessive expenditure of time and effort for a minimal increase of useful

information.

Quality Control (QC)

Field Blank SPMDs. Two field blank SPMDs (one with and one without PRCs) accompanied

each set of SPMDs (n = 5) deployed at each study site. Field-blank SPMDs were used to

determine if SPMDs were contaminated or losses of PRCs occurred during transport,

deployment and retrieval. The field-blank SPMDs were treated the same as the deployed

devices (more specifically, field blanks were exposed to study site air during the intervals of

time required to mount, deploy and retrieve SPMDs from the various exposure sites), except

that they were not exposed to study-site water. During the exposure intervals, field-blank

SPMDs were sealed back in the same shipping cans and stored frozen by VDEQ personnel.

The primary purpose of PRC spiked field-blanks is to provide a sample representative of the

amount (No) of individual PRCs present in SPMDs at time zero (see Equation 10 in section

on “Estimation of Water Concentrations from SPMD Levels”). Field blanks were processed

and analyzed exactly like exposed SPMDs.

SPMD Fabrication Blanks. Fabrication blanks were individual SPMDs, prepared as part of a

batch of SPMDs used in this study, which are identical to deployed SPMDs but lack PRCs.

They were maintained frozen at –10 to −20 °C in the laboratory (sealed in metal cans under

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argon) until the analysis of the exposed SPMDs. Processing and analysis of SPMD-

fabrication blanks was concurrent with and identical to that of deployed SPMDs. The

primary purpose of these QC samples was to account for any background contribution due to

interferences present in SPMD components, and to account any for contamination incurred

during laboratory storage, processing, and analytical procedures.

SPMD Process and Reagent Blanks. Process blanks consisted of a batch of SPMDs similar to

those used in the study, but made just prior to initiation of the analysis of an SPMD sample

set. Operationally, the only difference between SPMD-process blanks and SPMD-fabrication

blanks is the time of preparation and the lack of a storage period. Process blank SPMDs were

used for surrogate spikes to determine analyte recovery and the precision of the overall

analytical method.

Reagent blanks were aliquots of all solvents (volumes identical to those used for SPMD

samples) used during the processing, enrichment, and instrumental analysis of SPMD

samples, that were carried along with SPMD samples through the entire analytical procedure.

The combination of reagent and process blanks provides information on any background due

to laboratory reagents and helps identify specific analytical steps that may contribute to

sample contamination.

QC Checks. Although all of the aforementioned blanks are checks on different aspects of QC,

we limit the use of “QC checks” to the following types of spikes: 1) daily (each operation

day) injection of a known quantity of 14C-surrogate (e.g., 14C-phenanthrene) to evaluate of

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the performance of and the recovery through the SEC system; 2) spikes (e.g., 14C-

phenanthrene) of SPMD blanks to monitor dialytic recovery of each set of exposed SPMDs

and to measure recovery through the dialysis, SEC, etc. steps, and 3) SPMD process blanks,

spiked with the entire suite of target compounds (Table 1), which enable determination of the

recoveries of analytes through the entire processing, cleanup and fractionation procedures.

Thus, a QC check sample can represent individual cleanup and fractionation steps, as well as

the entire procedure. These QC samples are designed to demonstrate acceptable outcomes of

sample analyses (12).

Limits of Detection and Quantification. The method detection limit (MDL) and method

quantification limit (MQL) for analysis of SPMD samples were determined for each analyte

by measuring the values of coincident GC-ECD or GC-MSD peaks in all SPMD field blank

samples (n = 46) for each analyte. The MDL was operationally defined as the mean of field

blanks plus three-standard deviations. The MQL was operationally defined as the mean of

field blanks plus ten-standard deviations. For individual analytes having no coincident GC

peak, an assumed value equal to the low sample reject for the GC method (operationally

defined as 20 % of the concentration of the lowest standard concentration used for the GC-

calibration curve) was used to calculate the mean. In the cases where the calculated values of

the MQLs were below the level of the calibration curve employed in the GC-analysis, the

MQLs were set at the value of the lowest level of the calibration curve employed in

quantifying concentrations of an analyte (Table IV).

Data Reporting

21

Because the results of the analyses of SPMDs for trace and ultra-trace levels of organic

contaminants were to be directly imported into a modeling program used in a larger VDEQ

study, Mr. Roger Stewart of the VDEQ requested that data from this portion of the overall

study be reported as follows:

1) Values for the MDL and MQL will be determined for each targeted analyte and

these values will be reported in terms of ng/SPMD and estimated water concentration

(pg/L).

2) The results of all analyses will be given in numeric form, which can be directly

imported into the modeling program referred to above.

3) Water concentrations will be derived using our "Excel-based calculator”, which

applies specific equations noted in the subsequent section on the “Estimation of

Water Concentrations from SPMD Levels”.

4) If ng/SPMD concentrations, determined as described herein, are ≤ the analyte’s

MDLs for SPMD samples, values reported in Tables V and VI will default to the

MDL and these numbers will be italicized.

5) If SPMD concentrations, determined as described herein, are > than the MDL but ≤

the MQL for SPMD samples, values reported in Tables V and VI will be reported in

bold without the normal censoring of values ≤ MQL.

6) A footnote will be added to the bottom of each page of Tables V and VI to ensure

that the reader understands the meaning of bolded and the italicized entries.

Estimation of Water Concentrations from SPMD Amounts

22

In order to estimate water concentrations from SPMD amounts with a reasonable degree of

certainty, several conditions must be met. First, the amounts of targeted contaminants and

one or more PRCs must be accurately measured in exposed SPMDs. Second, appropriate

calibration data for both target compounds and PRCs must be available. Third, site specific in

situ sampling rates must be derived for target compounds using exposure adjustment factors

(EAFs; see Equation 11). The EAF is a site specific ratio that is approximately equivalent to

the in situ sampling rate of a selected PRC divided by the sampling rate of the same PRC

from calibration data (6). A large amount of SPMD-calibration data is available along with

the equations needed for estimating water concentrations from SPMD data (10). Measured

amounts of PRCs and analytes in SPMD samples, and previously reported equations and

calibration data (2, 5, 6), were used too extrapolate the concentrations of dissolved-phase

(i.e., concentration of residues that are readily available) contaminants in water from study

sites. Because the exchange of hydrophobic chemicals by SPMDs has been shown to be

isotropic (2, 5, 6) the following first-order equation can be used to describe the overall

accumulation of residues by SPMDs.

N = VsKswCw (1−exp[−Rst/VsKsw]) (1)

and

Cw = N/(VsKsw[1−exp(−Rst/VsKsw)]) (2)

where N is the amount of the chemical sampled by an SPMD (typically ng), Vs is the volume

of an SPMD (L), Ksw is the equilibrium SPMD-water partition coefficient (unitless), Cw is the

23

concentration of the chemical in ambient water, Rs is the SPMD sampling rate (L/d) and t is

the exposure time (d). Equations 1 and 2 are more familiar when the exponent is given as ket,

where ke is the loss or dissipation rate constant (t-1). Thus, ke is

ke = Rs/KswVs (3)

Equations 1 and 2 can be used for all three uptake phases of SPMDs, which include linear,

curvilinear and equilibrium. During the linear uptake phase the exponent Rst/KswVs is << 1

and the uptake rate constant is Rs/Vs. In this case, Equation 2 reduces to

Cw = N/Rst (4)

When Equation 4 applies, sampling is integrative or the amount of residues accumulated are

additive and water concentrations represent TWAs. Typically, SPMD sampling is in the

linear phase of uptake for compounds with log Kow values ≥ 5.0 and exposures periods of up

to one month.

In the case where the exponent Rst/KswVs is >> 1, equilibrium is attained and Equation 2

reduces to

Cw = N/KswVs (5)

24

Targeted chemicals have reached their maximum concentrations in SPMDs for a particular

exposure concentration, when Equation 5 applies to SPMD data. Typically, SPMD sampling

is in the equilibrium phase of uptake for compounds with log Kows ≤ 4.0 and exposure

periods of one month or more.

When SPMDs are in the curvilinear region of uptake Equations 2 must be used as is to

estimate Cw. In terms of first-order halflives (t1/2s), the curvilinear phase of chemical uptake

is operationally defined as the region time that exists between one t1/2 and four t1/2s. Note that

for first-order kinetics, one t1/2 is equivalent to

t1/2 = 0.693 KswVs/(Rs EAF) (6)

and four t1/2s are equivalent to

4t1/2 = 2.772 KswVs/(Rs EAF) (7)

In this study, Cw was determined by Equation 4 when exposure time was ≤ one t1/2 of an

analyte, Equation 5 when exposure time was ≥ four t1/2s of an analyte, and Equation 2 when

exposure time was between one and four t1/2s of an analyte. Estimation of a chemical’s in situ

t1/2 in an SPMD and its ambient Cw at each sample site requires the derivation of the EAF

(see Equation 11 below), as described by Huckins et al. (6). A key feature of the EAF is that

it is relatively constant for all chemicals that have the same rate-limiting barrier to uptake.

Measurement of the amount of a suitable PRC at the beginning and end of the exposure

25

period is the first step in this process. The following equations are used to estimate the EAF

for each exposure site.

N = No exp(−kept) (8)

and by substituting the group RsP/KswVs (Equation 3) for ke

N = No exp (−RsPt/KswVs) (9)

Solving for RsP

Rsp = KswVs −(ln [N/No])/t (10)

and

EAF ≈ RsP/RsC (11)

Where No is the amount of a PRC in an SPMD just before deployment, N is the amount of

PRC remaining in the SPMD following the exposure, RsP is the calculated SPMD sampling

rate for a PRC under a specific set of field or site conditions and RsC is the measured

sampling rate (i.e., from SPMD calibration studies) of the native equivalent of the deuterated

PRC. Then the in situ or site specific sampling rate (Rsi) of an analyte is the EAF times its

laboratory calibration Rs. Finally, an earlier study (6) has found that water concentration

estimates based on EAFs were within two-fold of independently measured values.

26

Before SPMD uptake rates can be estimated from and PRC loss rates, Ksw must be known or

calculated for contaminants of interest. The finding that Ksw is independent of temperature

between 2 °C and 30 °C (11) greatly simplifies the determination of analyte Ksw values. In

this study, two separate regression equations were required for the calculation Ksws (5, 6)

log KLw = –0.1257 (log Kow)2 + 1.9405 (log Kow ) –1.46 (12)

and

log Kmw = –0.0956 (log Kow)2 + 1.7643 (log Kow) –1.98 (13)

and

Ksw = (KLwVL + KmwVm)/Vs (14)

where KLw is the equilibrium lipid (triolein)-water partition coefficient, Kmw is the

equilibrium membrane (LDPE)-water partition coefficient, VL is the volume of lipid in the

SPMD, and Vm is the volume of membrane. The standard deviations (S.D.s) for the fits of

Equations 12 and 13 to literature data were 0.18 and 0.23, respectively. Equations 2, 4-8, and

10-14 have been incorporated into an Excel based calculator (5) for the estimation of water

concentrations and the calculator was used for water concentration estimates in this work

(see results in Table VI).

At this writing, a regression model has been developed (10) that combines data from

Equations 12-14.

log Ksw = –0.1618(log Kow)2 + 2.321 log Kow + ao (15)

27

where ao is –2.61 for nonpolar compounds and –3.20 for moderately polar pesticides. The

S.D. of the fit is 0.25 and the correlation coefficient r2 = 0.94. Equation 15 will greatly

simplify computation of Ksws in future studies.

RESULTS AND DISCUSSIONS

QC of Analytical Procedures

During cleaning of exposed SPMDs no holes were found in the membranes, demonstrating

that the deployment cages used by VDEQ personnel prevented punctures of the SPMDs

during exposures that lasted as long as 86 days. Also, amounts sufficient to quantify at least

one PRC (typically pyrene or phenanthrene) remained in SPMD samples, at the end of all

exposure periods. Visual inspection of SPMDs during processing indicated that membrane

biofouling varied with site and exposure duration, but no attempt was made to quantify these

apparent differences, because biofouling impedance of residue uptake is largely reflected by

the magnitude of PRC sampling rates at a particular site.

SPMD Field blanks exhibited no coincident GC peaks at levels significantly higher than

those associated with SPMD fabrication blanks and process blanks (i.e., controls). This

finding demonstrated that no inadvertent SPMD contamination occurred during storage,

shipping, deployment and retrieval. Thus, residues above those quantified in field-blank

SPMDs did indeed originate from the water of study sites. During the processing and cleanup

of samples, QC check samples for dialytic recovery, SEC performance, etc., and spiked

SPMD blank samples for overall method recoveries gave results which were consistent with

28

control limits (13) established at CERC for these processes (Figure 1). Furthermore, the QC

results for this work are similar to published results associated with the use of SPMDs (12).

Table VII provides a summery of these recovery results.

PRC Data

Exposure conditions and exposure times varied widely in this study (Table III). To reduce the

probability of scenarios where the amount of PRC residues remaining in SPMDs after

exposures is too little or too great to measure significant differences between time zero and

final concentrations, we choose five deuterated PAHs for this study with a 10-fold range in

their Kows (i.e., log Kow of acenaphthylene-d10 ≈ 4.0 and log Kow of pyrene-d10 ≈ 5.0).

Because the rates of release of hydrophobic organic compounds from SPMDs are inversely

proportional to compound Kow (2, 5, 6, 10), it seemed probable that the concentration of at

least one of the five PRCs used would be representative of a 20 to 80 % change in the time

zero concentration (i.e., the criteria proposed by Huckins et al [5] for the acceptability of

PRC data). The upper limit of an acceptable change from time zero concentration was set at

80 % because of the concern that concentrations would fall below the MQL for the PRC.

Generally, concentrations of acenaphthylene-d10, acenaphthene-d10, and fluorene-d10 in

exposed SPMDs were below their MQLs at all sites. Although these PRCs could not be used

for the determination of EAFs, their almost complete dissipation suggest that target

compounds with equivalent Kows would have approached or attained equilibrium during

these exposures. Concentrations of phenanthrene-d10 or pyrene-d10 in SPMDs were well

above the MQLs at all sites except 42 (2-CAT026.55) and they represented a 49-93 %

change from time zero concentrations. Therefore, either phenanthrene-d10 or pyrene-d10 was

29

used to calculate EAFs at exposure sites. Coincidentally, phenanthrene-d10 was used at half

the sites and pyrene-d10 was used at the other half. In Table VIII, the results of phenanthrene-

d10 or pyrene-d10 analyses are given in terms of release rate constants or keP, which is

equivalent to RsP/KswVs. Values of kePs can be readily converted into in situ RsPs by the

following equation

RsP = kePKswVs (16)

Interpretation of the keP data presented in Table VIII is complicated by the fact that two

deployments were made during this study and no measurements of stream flow rates were

obtained at the 46 sites. The first SPMD deployment was conducted in late spring and

summer, when the mean temperature was ≈ 15 °C (Table III), while the second SPMD

deployment was conducted in the fall to early winter, when the mean temperature was ≈ 10

°C (Table III). Furthermore, phenanthrene-d10 was used for all seven sites sampled in the

second SPMD deployment, where exposure temperatures were clearly lower.

Values of phenanthrene-d10 and pyrene-d10 kePs ranged from 0.0053 to 0.0552 (≈ 10-fold

difference) and from 0.0048 to 0.0504 (≈ 10-fold difference), respectively. A number of the

kePs of phenanthrene-d10 and pyrene-d10 appear to be significantly different than the keCs of

native phenanthrene and pyrene determined in laboratory calibration studies (5). The

calibration data (kecs or Rscs) used for PRCs were generated under conditions as follows: a

flow velocity of 0.004 cm/sec and at temperatures of 10, 18 and 26 °C (5). The magnitudes

of phenanthrene-d10 and pyrene-d10 kePs are similar, but the escaping tendency of

30

phenanthrene in SPMDs should be about 1.6 times as great as pyrene at temperatures ≥10

and ≤ 18 °C (5). However, phenanthrene-d10 was used as the PRC for all seven samples

recovered from the second SPMD deployment, where exposure temperatures were

significantly cooler. Significant differences in temperature can affect the magnitude of PRC

kePs (5) but the effects of differences in flow-turbulence at the membrane surface are

generally much greater.

Comments on SPMD Concentration Data

The results of the analyses of SPMDs exposed to river water in the Commonwealth of

Virginia are given in Table V. These data have been corrected for the backgrounds of

appropriate field blank samples. Important comments related to tabular values that are bolded

and italicized are given in the “Data Reporting” section. The primary purpose of this study

was to provide information as to the distribution of contaminants in the river waters of the

Commonwealth of Virginia. Data in Table V is reported to the nearest 0.01 ng/SPMD, where

censoring for number of significant figures was not performed. The rationale behind

disregarding the numbers of significant figures justified in Table V (at best only two

significant figures based on analytical methods) is that it permits a semi-quantitative ranking

of contaminants; 1) in the range between the MDL and MQL, and 2) at or near the lower

limits of quantification.

Observations Related to SPMD Concentrations

A number of OCPs and PAHs were detected in SPMDs at all sites (Table 5). However, only

pentachloroanisole (PCA) was found at quantifiable levels at every site analyzed. Although

31

PCA is classified as an OCP, it is produced in water by the microbial methylation of the

wood-preservative pentachlorophenol. Figure 2 shows how PCA concentrations in SPMDs

vary from site to site. Many of the sites also had elevated levels of some of the other OCPs,

which include the chlordanes, the nonachlors, hexachlorobenzene, dieldrin and endrin. The

amount of methoxychlor in SPMDs was quantifiable at only six sites, but one site (ID 9-

SNK019.59) was ≥ eight-fold times higher (37. 4 ng/SPMD) than any other site. Every one

of the six targeted current-use pesticides was detected in SPMDs at one or more of the 46

exposure sites. Diazinon was detected in SPMDs more frequently (25 of the 46 sites) than

any other current-use pesticide and the amounts were generally greater than others of this

class. However, diazinon levels typically fell between the MDL and MQL (2.4 and 18.2

ng/SPMD, respectively) of the pesticide. Although the amounts of endosulfan/endosulfan-II

in SPMDs were above their MQLs (2.6/1.8 ng/SPMD) at 20 of the 46 sites, these levels were

not as high as diazinon. The highest amounts of individual PAHs in SPMDs were

phenanthrene, fluoranthene and pyrene. This observation is typical of published data on PAH

concentrations in environmental waters and these chemicals generally originate from

pyrogenic sources. Because of the toxicity and ubiquitous distribution of phenanthrene,

fluoranthene and pyrene, they are listed by the US Environmental Protection Agency as

priority pollutants. In several cases, methylated PAHs were observed as well, which are

characteristic of petrogenic sources. Finally, PCBs were detected in SPMDs at only at two

sites and the amount of total congeners was greater than the MQL (64.5 ng/SPMD) at only

site ID 3-MTN003.31.

32

Observations related to Water Concentrations

A summary of the results of water concentration estimates is given in table VII. The

concentrations of diazinon in water from several sites approach or exceed ng/L. However,

this observation is generally based on SPMD concentrations that fall between the MDL and

MQL. The dissolved phase concentrations of several PP PAHs also approach or exceed ng/L

concentrations (e.g., site ID 3-MTN003.31). Of particular concern is that phototoxic

fluoranthrene and pyrene represent two of the three highest PAHs found in study waters. The

toxicity of these PAHs can be increased as much as 1000-fold by transient intermediates of

the PAH photooxidation process (14). For example, fluoranthrene has been shown to be toxic

to fish fry during solar radiation cycles, when water concentrations approach about 5-ng/L

(personal communication; James Oris, Miami University, Oxford, OH). Water concentrations

of total PCBs (2.1 ng/L) at the site identified above were elevated compared to the

background levels observed at all other sites.

ACKNOWLEDGEMENTS

We gratefully acknowledge the funding of the Virginia Department of Environmental

Quality and specifically the support of Roger Stewart and other Virginia Department of

Environmental Quality personnel involved in the deployment, retrieval, shipment, and

delivery of these samples to CERC for processing and analysis.

33

LITERATURE CITED

1. Huckins, J.N., Tubergen, M.W., Manuweera, G.K. 1990. Chemosphere 20: 533-553.

2. Huckins, J.N., Manuweera, G.K., Petty, J.D., MacKay, D., Lebo, J.A. 1993.

Environ. Sci. Technol. 27: 2489-2496.

3. Lebo, J.A., Gale, R.W., Petty, J.D., Huckins, J.N., Echols, K.R., Schroeder, D.J.,

Inmon, L.E. 1995. Environ. Sci. Technol., 29: 2886-2892.

4. Petty, J.D., Poulton, B.C., Charbonneau, C.S, Huckins, J.N., Jones, S.B., Cameron,

J.T., Prest, H.F. 1998. Environ. Sci. Technol. 32: 837-842.

5. Huckins, J.N., Petty, J.D., Prest, H.F., Clark, R.C., Alvarez, D.A., Orazio, C.E., Lebo,

J.A., Cranor, W.L., Johnson, B.T. A Guide for the Use of Semipermeable Membrane

Devices (SPMDs) as Samplers of Waterborne Hydrophobic Organic Contaminants;

Report for the American Petroleum Institute (API); API publication number 4690;

API: Washington, DC, 2002.

6. Huckins, J.N., Petty, J.D., Lebo, J.A., Almeida, F.V., Booij, K., Alvarez, D.A.,

Cranor, W.L., Clark, R.C., Mogensen, B. 2002. Environ. Sci. Technol. 36: 85-91.

7. Ellis, G.S., J.N. Huckins, C.E. Rostad, C.J. Schmitt, J.D. Petty, MacCarthy, P. 1995.

Environ. Toxicol. Chem. 14: 1875-1884.

8. Lebo, J.A., Almeida, F.V., Cranor, W.L., Petty, J.D., Huckins, J.N., Rastall, A.C.,

Alvarez, D.A., Mogensen, B.B., Johnson, B.T. 2004. Purification of Triolein for use

in Semipermeable Membrane Devices (SPMDs). Chemosphere 54: 1217-1224.

9. Huckins, J.N.; Petty, J.D.; Cranor, W.L.; Lebo, J.A.; Alvarez, D.A., Clark, R.C.

Evaluation of the Use of SPMDs for the Analysis of Hydrophobic Organic

34

Contaminants in Water of the Elizabeth River, Virginia. 2001. USGS Report was

Prepared for Virginia Department of Environmental Quality, Richmond, VA.

10. Huckins, J.N., Petty, J.D., Booij, K. 2005. Monitors of Organic Chemicals in the

Environment: Semipermeable Membrane Devices. Springer Publishing Company,

New York, NY, USA, In Press.

11. van Weerlee, E.M. 2003

12. DeVita, W.M., Crunkilton, R.L. 1998. Quality Control Associated with Use of

Semipermeable Membrane Devices. In E.E. Little First Editor, B.M. Greenburg

Second Editor and A.J. DeLonay, eds. Environ. Toxicol. and Risk Assess: Seventh

Volume. ASTM, West Conshohocken, PA. pp. 237-245.

13. Cranor, W.L., Alvarez, D.A., Huckins, J.N., Gale, R.W., Clark, R.C., Petty, J.D.,

Robertson, G.L. 2004. Sample Preparation and Data Quality Considerations for the

Analysis of Semipermeable Membrane Devices (SPMDs) Exposed to Air. Fourth

SETAC World Congress, November 14-18, Portland, OR.

14. Ramirez. M.H. 1997. Evaluation of the Acute and Chronic Toxicity of

Fluoranthrene-Spiked Sediments in the Presence of UV Light using the Amphipod

Hyalella azteca. Ph.D Thesis, Miami University, Oxford, OH.

35

Table I Target Analytes

Pesticides PAHs

Trifluralin Naphthalene

Hexachlorobenzene (HCB) Acenaphthylene

Pentachloroanisole (PCA) Acenaphthene

α-Benzenehexachloride (α-BHC) Fluorene

Diazinon Phenanthrene

Lindane Anthracene

β-Benzenehexachloride (β-BHC) Fluoranthene

Heptachlor Pyrene

δ-Benzenehexachloride (δ-BHC) Benz[a]anthracene

Dacthal Chrysene

Chlorpyrifos Benzo[b]fluoranthene

Oxychlordane Benzo[k]fluoranthene

Heptachlor Epoxide Benzo[a]pyrene

trans-Chlordane Indeno[1,2,3-c,d]pyrene

trans-Nonachlor Dibenz[a,h]anthracene

o,p’-DDE Benzo[g,h,i]perylene

cis-Chlordane Benzo[b]thiophene

Endosulfan 2-methylnaphthalene

p,p’-DDE 1-methylnaphthalene

Dieldrin Biphenyl

o,p’-DDD 1-ethylnaphthalene

Endrin 1,2-dimethylnaphthalene

cis-Nonachlor 4-methylbiphenyl

o,p’-DDT 2,3,5-trimethylnaphthalene

p,p’-DDD 1-methylfluorene

Endosulfan-II Dibenzothiophene

p,p’-DDT 2-methylphenanthrene

Endosulfan Sulfate 9-methylanthracene

Methoxychlor 3,6-dimethylphenanthrene

Mirex 2-methylfluoranthene

cis-Permethrin Benzo[b]naphtho[2,1-d]thiophene

trans-Permethrin Benzo[e]pyrene

Total PCBs Perylene

3-methylcholanthrene

36

Table II

Identification of Deployment Sites

CERC Site ID Station ID Name CERC Site ID Station ID Name

Site # 1 6-BCLN290.74 Site # 33 5-BPCT002.16 Site # 2 6-CNFH020.93 Site # 34 5-ABLC000.88 Site # 3 6-BPOW133.00 Site # 35 5-ANTW097.27 Site # 4 2-XUD000.15 Site # 36 9-NBS006.58 Site # 5 9-SNK019.59 Site # 37 5-AMHN097.83 Site # 8 4-ASRE020.75 Site # 38 2-NWD004.15 Site # 9 6-BPOW141.45 Site # 40 9-PLM000.35 Site # 10 2-MFK002.21 Site # 41 5-AFON024.32 Site # 12 6-ADI5013.73 Site # 42 2-CAT026.55 Site # 13 1-BSTH029.45 Site # 43 3-MTN003.31 Site # 15 1-AGAN000.32 Site # 44 9-DDD006.61 Site # 17 3-BLK001.92 Site # 45 4-ABWA008.53 Site # 18 2-XUE000.31 Site # 46 4-AMCG000.56 Site # 19 2-JK5070.97 Site # 48 4-ABOR033.22 Site # 21 3-CRC001.38 Site # 49 4-AFRY006.08 Site # 22 2-APP061.07 Site # 50 9-WLKO26.82 Site # 23 1-BNF5048.74 Site # 1 2-RVN022.61 Site # 24 8-MPN046.13 Site # 2 2-HAK004.34 Site # 25 2-BLB002.04 Site # 4 2-BLB002.04 Site # 28 3-JOA002.68 Site # 13 2-BLK001.92 Site # 29 1-ACAA000.83 Site # 14 4-AHRN007.65 Site # 31 8-MTA012.09 Site # 15 Not Given Site # 32 5-ASAP004.00 Site # 18 Not Given

37

Table III

Exposure Times and Temperatures

CERC VA DEQ # of days Average CERC VA DEQ # of days Average Site ID Station ID Deployed Temp ºC Site ID Station ID Deployed Temp ºC Site # 1 6-BCLN290.74 28 17 Site # 33 5-BPCT002.16 30 18 Site # 2 6-CNFH020.93 28 17 Site # 34 5-ABLC000.88 28 16 Site # 3 6-BPOW133.00 29 18 Site # 35 5-ANTW097.27 41 19 Site # 4 2-XUD000.15 33 15 Site # 36 9-NBS006.58 27 10 Site # 5 9-SNK019.59 27 15 Site # 37 5-AMHN097.83 49 19 Site # 8 4-ASRE020.75 35 15 Site # 38 2-NWD004.15 31 16 Site # 9 6-BPOW141.45 29 18 Site # 40 9-PLM000.35 29 11 Site # 10 2-MFK002.21 32 14 Site # 41 5-AFON024.32 46 20 Site # 12 6-ADI5013.73 28 15 Site # 42 2-CAT026.55 35 13 Site # 13 1-BSTH029.45 30 16 Site # 43 3-MTN003.31 61 22 Site # 15 1-AGAN000.32 29 10 Site # 44 9-DDD006.61 27 12 Site # 17 3-BLK001.92 32 17 Site # 45 4-ABWA008.53 28 15 Site # 18 2-XUE000.31 32 16 Site # 46 4-AMCG000.56 27 14 Site # 19 2-JK5070.97 30 13 Site # 48 4-ABOR033.22 28 15 Site # 21 3-CRC001.38 29 14 Site # 49 4-AFRY006.08 28 11 Site # 22 2-APP061.07 51 19 Site # 50 9-WLKO26.82 27 13 Site # 23 1-BNF5048.74 29 14 Site # 1 2-RVN022.61 60 11 Site # 24 8-MPN046.13 36 18 Site # 2 2-HAK004.34 35 9 Site # 25 2-BLB002.04 30 17 Site # 4 2-BLB002.04 32 9 Site # 28 3-JOA002.68 86 19 Site # 13 2-BLK001.92 28 11 Site # 29 1-ACAA000.83 28 15 Site # 14 4-AHRN007.65 30 9 Site # 31 8-MTA012.09 28 17 Site # 15 Not Given 30 10 Site # 32 5-ASAP004.00 50 19 Site # 18 Not Given 30 10

38

Table IV

MDL & MQL Values for Targeted Analytes

MDL MQL MDL MQL OCPs & PCBs ng/SPMD ng/SPMD PAHs ng/SPMD ng/SPMD Trifluralin 1.10 11.56 Naphthalene 46.94 123.71 Hexachlorobenzene 0.84 3.85 Acenaphthylene 4.00 20.00 Pentachloroanisole 0.79 3.67 Acenaphthene 18.63 58.11 α-Benzenehexachloride 1.34 10.25 Fluorene 18.63 58.11 Diazinon 2.45 18.20 Phenanthrene 69.87 200.15 Lindane 1.53 4.96 Anthracene 4.00 20.00 β-Benzenehexachloride 1.76 8.22 Fluoranthene 4.00 20.00 Heptachlor 0.12 0.92 Pyrene 9.18 29.60 δ-Benzenehexachloride 0.12 0.92 Benz[a]anthracene 4.00 20.00 Dacthal 0.36 1.70 Chrysene 88.45 232.28 Chlorpyrifos 1.12 5.02 Benzo[b]fluoranthene 4.00 20.00 Oxychlordane 1.75 8.20 Benzo[k]fluoranthene 4.00 20.00 Heptachlor Epoxide 2.55 11.05 Benzo[a]pyrene 4.00 20.00 trans-Chlordane 0.53 2.51 Indeno[1,2,3-c,d]pyrene 4.00 20.00 trans-Nonachlor 0.12 0.92 Dibenz[a,h]anthracene 4.00 20.00 o,p’-DDE 0.89 4.13 Benzo[g,h,i]perylene 9.18 29.60 cis-Chlordane 1.14 5.39 Benzo[b]thiophene 24.57 74.95 Endosulfan 0.55 2.64 2-methylnaphthalene 24.63 77.12 p,p’-DDE 1.71 5.63 1-methylnaphthalene 9.18 29.60 Dieldrin 1.22 5.66 Biphenyl 4.00 20.00 o,p’-DDD 1.60 7.60 1-ethylnaphthalene 4.00 20.00 Endrin 1.75 6.02 1,2-dimethylnaphthalene 4.00 20.00 cis-Nonachlor 1.81 7.91 4-methylbiphenyl 40.10 110.85 o,p’-DDT 1.30 6.15 2,3,5-trimethylnaphthalene 4.00 20.00 p,p’-DDD 1.28 5.62 1-methylfluorene 4.00 20.00 Endosulfan-II 0.39 1.83 Dibenzothiophene 4.00 20.00 p,p’-DDT 2.83 10.36 2-methylphenanthrene 4.00 20.00 Endosulfan Sulfate 0.70 3.26 9-methylanthracene 4.00 20.00 Methoxychlor 0.12 0.92 3,6-dimethylphenanthrene 4.00 20.00 Mirex 0.12 0.92 2-methylfluoranthene 4.00 20.00 cis-Permethrin 1.13 6.97 Benzo[b]naphtho[2,1-d]thiophene 4.00 20.00 trans-Permethrin 0.42 1.28 Benzo[e]pyrene 4.00 20.00 Total PCBs 14.09 64.52 Perylene 4.00 20.00 3-methylcholanthrene 4.00 20.00

NOTE: The MQL was set to the low standard in the calibration curve or the mean of all “Field Blank” background signals + 10 times their standard deviation (which ever was higher). The MDL was set to the mean of all “Field Blank” background signals + 3 times their standard deviation. In cases where there were no coincident peaks, the MDL was set to 20% of the MQL and the MQL was set to the low standard. All values are reported without censoring for significant figures (only two significant figures are justified).

39

Table V

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 1, Deployment # 1, Station ID 6-BCLN290.74

OCPs & PCBs Rep # 1 Rep # 2 Mean PAHs Rep # 1 Rep # 2 Mean Trifluralin 3.01 2.54 2.77 Naphthalene 46.94 46.94 46.94 Hexachlorobenzene 2.05 2.01 2.03 Acenaphthylene 4.00 4.00 4.00 Pentachloroanisole 6.82 6.80 6.81 Acenaphthene 20.00 18.63 18.63 α-Benzenehexachloride 1.34 1.34 1.34 Fluorene 20.00 20.00 20.00 Diazinon 2.45 2.45 2.45 Phenanthrene 210.00 160.00 185.00 Lindane 1.53 1.53 1.53 Anthracene 10.00 10.00 10.00 β-Benzenehexachloride 1.76 1.76 1.76 Fluoranthene 710.00 660.00 685.00 Heptachlor 1.20 0.12 0.60 Pyrene 420.00 400.00 410.00 δ-Benzenehexachloride 1.26 0.12 0.63 Benz[a]anthracene 40.00 30.00 35.00 Dacthal 0.36 0.36 0.36 Chrysene 190.00 190.00 190.00 Chlorpyrifos 2.44 2.67 2.56 Benzo[b]fluoranthene 60.00 60.00 60.00 Oxychlordane 4.05 3.88 3.97 Benzo[k]fluoranthene 30.00 30.00 30.00 Heptachlor Epoxide 5.26 5.18 5.22 Benzo[a]pyrene 10.00 10.00 10.00 trans-Chlordane 7.74 7.68 7.71 Indeno[1,2,3-c,d]pyrene 10.00 10.00 10.00 trans-Nonachlor 8.51 8.53 8.52 Dibenz[a,h]anthracene 4.00 4.00 4.00 o,p’-DDE 0.89 0.89 0.89 Benzo[g,h,i]perylene 10.00 10.00 10.00 cis-Chlordane 11.18 11.38 11.28 Benzo[b]thiophene 24.57 24.57 24.57 Endosulfan 3.03 2.81 2.92 2-methylnaphthalene 40.00 40.00 40.00 p,p’-DDE 1.71 1.71 1.71 1-methylnaphthalene 9.18 9.18 9.18 Dieldrin 11.99 12.50 12.25 Biphenyl 20.00 20.00 20.00 o,p’-DDD 12.56 12.75 12.66 1-ethylnaphthalene 4.00 4.00 4.00 Endrin 1.75 1.75 1.75 1,2-dimethylnaphthalene 10.00 10.00 10.00 cis-Nonachlor 2.48 2.94 2.71 4-methylbiphenyl 40.10 40.10 40.10 o,p’-DDT 1.30 1.30 1.30 2,3,5-trimethylnaphthalene 20.00 20.00 20.00 p,p’-DDD 4.46 4.94 4.70 1-methylfluorene 4.00 4.00 4.00 Endosulfan-II 0.79 0.39 0.40 Dibenzothiophene 4.00 4.00 4.00 p,p’-DDT 2.83 5.78 4.01 2-methylphenanthrene 4.00 4.00 4.00 Endosulfan Sulfate 0.70 0.79 0.70 9-methylanthracene 4.00 4.00 4.00 Methoxychlor 0.12 0.12 0.12 3,6-dimethylphenanthrene 4.00 4.00 4.00 Mirex 0.12 0.12 0.12 2-methylfluoranthene 4.00 4.00 4.00 cis-Permethrin 1.13 1.13 1.13 Benzo[b]naphtho[2,1-d]thiophene 4.00 4.00 4.00 trans-Permethrin 1.90 2.26 2.08 Benzo[e]pyrene 4.00 4.00 4.00 Total PCBs 14.09 14.09 14.09 Perylene 4.00 4.00 4.00 3-methylcholanthrene 4.00 4.00 4.00

NOTE: All values are reported without censoring for significant figures (two significant figures are justified). All values <MDL are reported as the MDL for that analyte and are italicized. All values >MDL and <MQL are reported without censoring for MQL and are bolded

40

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 2, Deployment # 1, Station ID 6-CNFH020.93



41

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 3, Deployment # 1, Station ID 6-BPOW133.00



42

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 4, Deployment # 1, Station ID 2-XUD000.15

OCPs & PCBs Rep # 1 Rep # 2 Mean PAHs Rep # 1 Rep # 2 Mean Trifluralin 6.53 6.81 6.67 Naphthalene 46.94 46.94 46.94 Hexachlorobenzene 5.46 5.58 5.52 Acenaphthylene 4.00 4.00 4.00 Pentachloroanisole 7.90 8.63 8.26 Acenaphthene 18.63 18.63 18.63 α-Benzenehexachloride 4.05 2.22 3.14 Fluorene 18.63 18.63 18.63 Diazinon 15.34 14.20 14.77 Phenanthrene 69.87 69.87 69.87 Lindane 3.02 2.42 2.72 Anthracene 4.00 4.00 4.00 β-Benzenehexachloride 1.76 1.76 1.76 10.00 10.00 10.00 Fluoranthene

0.68 0.76 0.72Heptachlor Pyrene 10.00 10.00 10.00 δ-Benzenehexachloride 0.12 0.12 0.12 Benz[a]anthracene 4.00 4.00 4.00 Dacthal 0.36 0.36 0.36 Chrysene 88.45 88.45 88.45 Chlorpyrifos 1.12 1.75 1.12 Benzo[b]fluoranthene 4.00 4.00 4.00 Oxychlordane 1.75 1.75 1.75 Benzo[k]fluoranthene 4.00 4.00 4.00 Heptachlor Epoxide 2.55 2.59 2.55 Benzo[a]pyrene 4.00 4.00 4.00 trans-Chlordane 1.31 2.44 1.88 Indeno[1,2,3-c,d]pyrene 4.00 4.00 4.00 trans-Nonachlor 1.21 1.96 1.58 Dibenz[a,h]anthracene 4.00 4.00 4.00 o,p’-DDE 0.89 0.89 0.89 Benzo[g,h,i]perylene 9.18 9.18 9.18 cis-Chlordane 1.82 2.59 2.20 Benzo[b]thiophene 24.57 24.57 24.57 Endosulfan 2.53 2.93 2.73 2-methylnaphthalene 24.63 24.63 24.63 p,p’-DDE 1.71 1.71 1.71 1-methylnaphthalene 9.18 9.18 9.18 Dieldrin 2.06 2.03 2.05 Biphenyl 4.00 4.00 4.00 o,p’-DDD 2.12 1.60 1.60 1-ethylnaphthalene 4.00 4.00 4.00 Endrin 1.80 2.24 2.02 1,2-dimethylnaphthalene 4.00 4.00 4.00 cis-Nonachlor 1.81 1.81 1.81 4-methylbiphenyl 40.10 40.10 40.10 o,p’-DDT 1.30 1.30 1.30 2,3,5-trimethylnaphthalene 10.00 10.00 10.00 p,p’-DDD 1.28 1.28 1.28 1-methylfluorene 4.00 4.00 4.00 Endosulfan-II 0.39 0.39 0.39 Dibenzothiophene 4.00 4.00 4.00 p,p’-DDT 2.83 5.27 3.85 2-methylphenanthrene 4.00 4.00 4.00 Endosulfan Sulfate 0.70 0.70 0.70 9-methylanthracene 4.00 4.00 4.00 Methoxychlor 0.12 0.12 0.12 3,6-dimethylphenanthrene 4.00 4.00 4.00 Mirex 0.12 0.12 0.12 2-methylfluoranthene 4.00 4.00 4.00 cis-Permethrin 1.13 1.13 1.13 Benzo[b]naphtho[2,1-d]thiophene 4.00 4.00 4.00 trans-Permethrin 1.05 2.10 1.57 Benzo[e]pyrene 4.00 4.00 4.00 Total PCBs 14.09 14.09 14.09 Perylene 4.00 4.00 4.00 3-methylcholanthrene 4.00 4.00 4.00


43

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 5, Deployment # 1, Station ID 9-SNK019.59



44

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 8, Deployment # 1, Station ID 4-ASRE020.75



45

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 9, Deployment # 1, Station ID 6-BPOW141.45



46

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 10, Deployment # 1, Station ID 2-MFK002.21



47

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 12, Deployment # 1, Station ID 6-ADI5013.73



48

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 13, Deployment # 1, Station ID 1-BSTH029.45

OCPs & PCBs Rep # 1 Rep # 2 Mean PAHs Rep # 1 Rep # 2 Mean Trifluralin 1.10 1.10 1.10 Naphthalene Lost 46.94 46.94 Hexachlorobenzene 1.53 2.22 1.88 Acenaphthylene Lost 4.00 4.00 Pentachloroanisole 10.97 15.87 13.42 Acenaphthene Lost 18.63 18.63 α-Benzenehexachloride 1.34 1.58 1.34 Fluorene Lost 18.63 18.63 Diazinon 10.51 21.44 15.97 Phenanthrene Lost 69.87 69.87 Lindane 2.43 3.50 2.97 Anthracene Lost 4.00 4.00 β-Benzenehexachloride 1.76 1.76 1.76 Fluoranthene Lost 80.00 80.00 Heptachlor 0.12 0.40 0.24 Pyrene Lost 150.00 150.00 δ-Benzenehexachloride 0.12 0.90 0.45 Benz[a]anthracene Lost 10.00 10.00 Dacthal 0.36 0.36 0.36 Chrysene Lost 88.45 88.45 Chlorpyrifos 13.80 23.61 18.70 Benzo[b]fluoranthene Lost 10.00 10.00 Oxychlordane 1.77 4.78 3.28 Benzo[k]fluoranthene Lost 10.00 10.00 Heptachlor Epoxide 2.55 4.46 3.33 Benzo[a]pyrene Lost 4.00 4.00 trans-Chlordane 2.94 5.63 4.29 Indeno[1,2,3-c,d]pyrene Lost 4.00 4.00 trans-Nonachlor 3.94 6.85 5.40 Dibenz[a,h]anthracene Lost 4.00 4.00 o,p’-DDE 0.89 0.89 0.89 Benzo[g,h,i]perylene Lost 9.18 9.18 cis-Chlordane 4.12 6.35 5.24 Benzo[b]thiophene Lost 24.57 24.57 Endosulfan 3.01 4.25 3.63 2-methylnaphthalene Lost 24.63 24.63 p,p’-DDE 4.76 5.84 5.30 1-methylnaphthalene Lost 10.00 10.00 Dieldrin 10.50 12.49 11.49 Biphenyl Lost 4.00 4.00 o,p’-DDD 5.83 8.19 7.01 1-ethylnaphthalene Lost 4.00 4.00 Endrin 1.75 1.75 1.75 1,2-dimethylnaphthalene Lost 4.00 4.00 cis-Nonachlor 1.81 2.30 1.81 4-methylbiphenyl Lost 40.10 40.10 o,p’-DDT 1.30 3.44 1.72 2,3,5-trimethylnaphthalene Lost 4.00 4.00 p,p’-DDD 3.38 10.77 7.08 1-methylfluorene Lost 4.00 4.00 Endosulfan-II 0.39 0.39 0.39 Dibenzothiophene Lost 4.00 4.00 p,p’-DDT 3.64 15.39 9.52 2-methylphenanthrene Lost 4.00 4.00 Endosulfan Sulfate 0.70 0.70 0.70 9-methylanthracene Lost 4.00 4.00 Methoxychlor 0.12 1.17 0.59 3,6-dimethylphenanthrene Lost 4.00 4.00 Mirex 0.12 0.12 0.12 2-methylfluoranthene Lost 4.00 4.00 cis-Permethrin 1.13 1.13 1.13 Benzo[b]naphtho[2,1-d]thiophene Lost 4.00 4.00 trans-Permethrin 0.42 0.42 0.42 Benzo[e]pyrene Lost 10.00 10.00 Total PCBs 14.09 14.09 14.09 Perylene Lost 4.00 4.00 3-methylcholanthrene Lost 4.00 4.00


49

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 15, Deployment # 1, Station ID 1-AGAN000.32

OCPs & PCBs Rep # 1 Rep # 2 Mean PAHs Rep # 1 Rep # 2 Mean Trifluralin 1.10 1.54 1.10 Naphthalene 46.94 46.94 46.94 Hexachlorobenzene 1.29 1.40 1.35 Acenaphthylene 4.00 4.00 4.00 Pentachloroanisole 17.21 18.04 17.63 Acenaphthene 18.63 20.00 18.63 α-Benzenehexachloride 1.34 1.34 1.34 Fluorene 18.63 18.63 18.63 Diazinon 2.45 2.82 2.45 Phenanthrene 69.87 70.00 69.87 Lindane 1.53 1.53 1.53 Anthracene 4.00 4.00 4.00 β-Benzenehexachloride 1.76 1.76 1.76 Fluoranthene 120.00 40.00 80.00 Heptachlor 0.12 0.12 0.12 Pyrene 210.00 20.00 115.00 δ-Benzenehexachloride 0.12 0.12 0.12 Benz[a]anthracene 10.00 4.00 5.00 Dacthal 0.36 0.36 0.36 Chrysene 88.45 88.45 88.45 Chlorpyrifos 4.02 6.29 5.15 Benzo[b]fluoranthene 20.00 4.00 10.00 Oxychlordane 3.86 1.75 2.71 Benzo[k]fluoranthene 10.00 4.00 5.00 Heptachlor Epoxide 4.07 2.55 3.31 Benzo[a]pyrene 10.00 4.00 5.00 trans-Chlordane 6.31 4.34 5.33 Indeno[1,2,3-c,d]pyrene 4.00 4.00 4.00 trans-Nonachlor 7.01 5.22 6.12 Dibenz[a,h]anthracene 4.00 4.00 4.00 o,p’-DDE 0.89 0.89 0.89 Benzo[g,h,i]perylene 9.18 9.18 9.18 cis-Chlordane 8.53 7.82 8.18 Benzo[b]thiophene 24.57 24.57 24.57 Endosulfan 5.00 4.12 4.56 2-methylnaphthalene 24.63 24.63 24.63 p,p’-DDE 19.11 20.36 19.73 1-methylnaphthalene 9.18 9.18 9.18 Dieldrin 13.21 12.56 12.88 Biphenyl 4.00 4.00 4.00 o,p’-DDD 5.48 1.60 2.97 1-ethylnaphthalene 4.00 4.00 4.00 Endrin 17.66 11.54 14.60 1,2-dimethylnaphthalene 4.00 4.00 4.00 cis-Nonachlor 2.69 1.81 1.81 4-methylbiphenyl 40.10 40.10 40.10 o,p’-DDT 3.66 1.30 1.83 2,3,5-trimethylnaphthalene 4.00 4.00 4.00 p,p’-DDD 6.26 2.98 4.62 1-methylfluorene 4.00 4.00 4.00 Endosulfan-II 0.39 0.39 0.39 Dibenzothiophene 4.00 4.00 4.00 p,p’-DDT 8.22 5.07 6.65 2-methylphenanthrene 10.00 4.00 5.00 Endosulfan Sulfate 0.70 0.70 0.70 9-methylanthracene 4.00 4.00 4.00 Methoxychlor 0.12 0.12 0.12 3,6-dimethylphenanthrene 4.00 4.00 4.00 Mirex 0.12 0.12 0.12 2-methylfluoranthene 10.00 4.00 5.00 cis-Permethrin 1.13 1.13 1.13 Benzo[b]naphtho[2,1-d]thiophene 4.00 4.00 4.00 trans-Permethrin 0.42 0.42 0.42 Benzo[e]pyrene 10.00 4.00 5.00 Total PCBs 14.09 14.09 14.09 Perylene 4.00 10.00 5.00 1.10 1.54 1.10 3-methylcholanthrene 4.00 4.00 4.00


50

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 17, Deployment # 1, Station ID 3-BLK001.92



51

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 18, Deployment # 1, Station ID 2-XUE000.31



52

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 19, Deployment # 1, Station ID 2-JK5070.97



53

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 21, Deployment # 1, Station ID 3-CRC001.38



54

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 22, Deployment # 1, Station ID 2-APP061.07



55

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 23, Deployment # 1, Station ID 1-BNF5048.74

OCPs & PCBs Rep # 1 Rep # 2 Mean PAHs Rep # 1 Rep # 2 Mean Trifluralin 1.10 1.10 1.10 Naphthalene 46.94 46.94 46.94 Hexachlorobenzene 1.39 3.75 2.57 Acenaphthylene 4.00 4.00 4.00 Pentachloroanisole 2.06 10.05 6.06 Acenaphthene 18.63 18.63 18.63 α-Benzenehexachloride 1.34 1.34 1.34 Fluorene 20.00 18.63 18.63 Diazinon 2.45 2.45 2.45 Phenanthrene 100.00 70.00 85.00 Lindane 1.53 1.53 1.53 Anthracene 4.00 4.00 4.00 β-Benzenehexachloride 2.04 1.76 1.76 Fluoranthene 70.00 70.00 70.00

0.15 0.23 0.19Heptachlor Pyrene 60.00 50.00 55.00 δ-Benzenehexachloride 3.46 0.12 1.73 Benz[a]anthracene 4.00 4.00 4.00 Dacthal 0.36 0.36 0.36 Chrysene 88.45 88.45 88.45 Chlorpyrifos 1.21 1.41 1.31 Benzo[b]fluoranthene 4.00 4.00 4.00 Oxychlordane 1.75 1.75 1.75 Benzo[k]fluoranthene 4.00 4.00 4.00 Heptachlor Epoxide 2.55 2.55 2.55 Benzo[a]pyrene 4.00 4.00 4.00 trans-Chlordane 1.94 2.88 2.41 Indeno[1,2,3-c,d]pyrene 4.00 4.00 4.00 trans-Nonachlor 0.86 1.86 1.36 Dibenz[a,h]anthracene 4.00 4.00 4.00 o,p’-DDE 0.89 0.89 0.89 Benzo[g,h,i]perylene 9.18 9.18 9.18 cis-Chlordane 1.93 3.08 2.50 Benzo[b]thiophene 24.57 24.57 24.57 Endosulfan 0.55 0.90 0.55 2-methylnaphthalene 24.63 24.63 24.63 p,p’-DDE 9.13 14.43 11.78 1-methylnaphthalene 10.00 9.18 9.18 Dieldrin 2.75 3.44 3.09 Biphenyl 4.00 4.00 4.00 o,p’-DDD 2.78 14.77 8.78 1-ethylnaphthalene 4.00 4.00 4.00 Endrin 1.75 3.87 1.93 1,2-dimethylnaphthalene 4.00 4.00 4.00 cis-Nonachlor 1.81 1.81 1.81 4-methylbiphenyl 40.10 40.10 40.10 o,p’-DDT 1.51 4.02 2.77 2,3,5-trimethylnaphthalene 20.00 4.00 10.00 p,p’-DDD 1.33 3.93 2.63 1-methylfluorene 4.00 4.00 4.00 Endosulfan-II 0.46 2.53 1.49 Dibenzothiophene 4.00 4.00 4.00 p,p’-DDT 2.83 7.69 5.09 2-methylphenanthrene 30.00 10.00 20.00 Endosulfan Sulfate 0.70 0.70 0.70 9-methylanthracene 4.00 4.00 4.00 Methoxychlor 0.12 0.12 0.12 3,6-dimethylphenanthrene 4.00 4.00 4.00 Mirex 0.12 0.12 0.12 2-methylfluoranthene 4.00 4.00 4.00 cis-Permethrin 1.13 1.13 1.13 Benzo[b]naphtho[2,1-d]thiophene 4.00 4.00 4.00 trans-Permethrin 0.42 0.42 0.42 Benzo[e]pyrene 4.00 4.00 4.00 Total PCBs 14.09 14.09 14.09 Perylene 10.00 10.00 10.00 3-methylcholanthrene 4.00 4.00 4.00


56

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 24, Deployment # 1, Station ID 8-MPN046.13



57

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 25, Deployment # 1, Station ID 2-BLB002.04



58

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 28, Deployment # 1, Station ID 3-JOA002.68



59

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 29, Deployment # 1, Station ID 1-ACAA000.83



60

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 31, Deployment # 1, Station ID 8-MTA012.09



61

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 32, Deployment # 1, Station ID 5-ASAP004.00



62

Table V (continued)

Result of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 33, Deployment # 1, Station ID 5-BPCT002.16


0.12 0.12 Heptachlor 0.12 Pyrene 110.00 110.00 110.00 δ-Benzenehexachloride 0.12 0.12 0.12 Benz[a]anthracene 4.00 4.00 4.00 Dacthal 0.92 0.43 0.68 Chrysene 88.45 88.45 88.45 Chlorpyrifos 4.89 3.85 4.37 Benzo[b]fluoranthene 4.00 4.00 4.00 Oxychlordane 1.75 1.75 1.75 Benzo[k]fluoranthene 4.00 4.00 4.00 Heptachlor Epoxide 2.55 2.55 2.55 Benzo[a]pyrene 4.00 4.00 4.00 trans-Chlordane 2.12 2.02 2.07 Indeno[1,2,3-c,d]pyrene 4.00 4.00 4.00 trans-Nonachlor 1.09 1.01 1.05 Dibenz[a,h]anthracene 4.00 4.00 4.00 o,p’-DDE 0.89 0.89 0.89 Benzo[g,h,i]perylene 9.18 9.18 9.18 cis-Chlordane 3.26 3.57 3.42 Benzo[b]thiophene 24.57 24.57 24.57 Endosulfan 0.79 0.92 0.86 2-methylnaphthalene 24.63 24.63 24.63 p,p’-DDE 41.53 39.52 40.52 1-methylnaphthalene 30.00 30.00 30.00 Dieldrin 25.98 25.99 25.99 Biphenyl 4.00 4.00 4.00 o,p’-DDD 5.94 6.90 6.42 1-ethylnaphthalene 4.00 4.00 4.00 Endrin 7.96 8.23 8.10 1,2-dimethylnaphthalene 4.00 4.00 4.00 cis-Nonachlor 1.81 1.81 1.81 4-methylbiphenyl 40.10 40.10 40.10 o,p’-DDT 3.87 3.99 3.93 2,3,5-trimethylnaphthalene 10.00 10.00 10.00 p,p’-DDD 38.46 39.03 38.74 1-methylfluorene 10.00 10.00 10.00 Endosulfan-II 2.68 2.45 2.57 Dibenzothiophene 10.00 10.00 10.00 p,p’-DDT 14.02 14.51 14.26 2-methylphenanthrene 10.00 10.00 10.00 Endosulfan Sulfate 0.80 1.04 0.92 9-methylanthracene 4.00 4.00 4.00 Methoxychlor 0.12 0.12 0.12 3,6-dimethylphenanthrene 4.00 10.00 5.00 Mirex 0.12 0.12 0.12 2-methylfluoranthene 4.00 4.00 4.00 cis-Permethrin 1.13 1.13 1.13 Benzo[b]naphtho[2,1-d]thiophene 4.00 4.00 4.00 trans-Permethrin 0.42 0.42 0.42 Benzo[e]pyrene 4.00 4.00 4.00 Total PCBs 14.09 14.09 14.09 Perylene 20.00 20.00 20.00 3-methylcholanthrene 4.00 4.00 4.00


63

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 34, Deployment # 1, Station ID 5-ABLC000.88



64

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 35, Deployment # 1, Station ID 5-ANTW097.27



65

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 36, Deployment # 1, Station ID 9-NBS006.58



66

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 37, Deployment # 1, Station ID 5-AMHN097.83



67

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background CERC Site # 38, Deployment # 1, Station ID 2-NWD004.15



68

Table V (continued)

Results of SPMD Analysis (ng/SPMD) Corrected for Background

CERC Site # 40, Deployment # 1, Station ID 9-PLM000.35



69

Table V (continued)


CERC Site # 41, Deployment # 1, Station ID 5-AFON024.32


0.12 0.12 0.12 20.00 Heptachlor Pyrene 20.00 20.00 δ-Benzenehexachloride 0.12 0.12 0.12 Benz[a]anthracene 4.00 4.00 4.00 Dacthal 0.36 0.36 0.36 Chrysene 88.45 88.45 88.45 Chlorpyrifos 1.12 1.12 1.12 Benzo[b]fluoranthene 4.00 4.00 4.00 Oxychlordane 1.75 1.75 1.75 Benzo[k]fluoranthene 4.00 4.00 4.00 Heptachlor Epoxide 2.55 2.55 2.55 Benzo[a]pyrene 4.00 4.00 4.00 trans-Chlordane 0.71 0.58 0.65 Indeno[1,2,3-c,d]pyrene 4.00 4.00 4.00 trans-Nonachlor 0.49 0.12 0.31 Dibenz[a,h]anthracene 4.00 4.00 4.00 o,p’-DDE 0.89 0.89 0.89 Benzo[g,h,i]perylene 9.18 9.18 9.18 cis-Chlordane 1.17 1.14 1.14 Benzo[b]thiophene 24.57 24.57 24.57 Endosulfan 0.55 0.55 0.55 2-methylnaphthalene 24.63 24.63 24.63 p,p’-DDE 8.33 5.58 6.96 1-methylnaphthalene 9.18 9.18 9.18 Dieldrin 3.16 2.00 2.58 Biphenyl 4.00 4.00 4.00 o,p’-DDD 1.60 1.60 1.60 1-ethylnaphthalene 4.00 4.00 4.00 Endrin 1.75 1.75 1.75 1,2-dimethylnaphthalene 4.00 4.00 4.00 cis-Nonachlor 1.81 1.81 1.81 4-methylbiphenyl 40.10 40.10 40.10 o,p’-DDT 1.30 1.30 1.30 2,3,5-trimethylnaphthalene 4.00 4.00 4.00 p,p’-DDD 2.72 2.67 2.70 1-methylfluorene 4.00 4.00 4.00 Endosulfan-II 1.07 1.19 1.13 Dibenzothiophene 4.00 4.00 4.00 p,p’-DDT 4.41 3.99 4.20 2-methylphenanthrene 4.00 4.00 4.00 Endosulfan Sulfate 0.70 0.70 0.70 9-methylanthracene 4.00 4.00 4.00 Methoxychlor 0.12 0.12 0.12 3,6-dimethylphenanthrene 4.00 4.00 4.00 Mirex 0.12 0.12 0.12 2-methylfluoranthene 4.00 4.00 4.00 cis-Permethrin 1.13 1.13 1.13 Benzo[b]naphtho[2,1-d]thiophene 4.00 4.00 4.00 trans-Permethrin 0.42 0.42 0.42 Benzo[e]pyrene 4.00 4.00 4.00 Total PCBs 14.09 14.09 14.09 Perylene 20.00 10.00 15.00 3-methylcholanthrene 4.00 4.00 4.00


70

Table V (continued)


CERC Site # 42, Deployment # 1, Station ID 2-CAT026.55



71

Table V (continued)


CERC Site # 43, Deployment # 1, Station ID 3-MTN003.31

OCPs & PCBs Rep # 1 Rep # 2 Mean PAHs Rep # 1 Rep # 2 Mean Trifluralin 1.37 1.63 1.50 Naphthalene 46.94 46.94 46.94 Hexachlorobenzene 3.50 3.73 3.61 Acenaphthylene 4.00 4.00 4.00 Pentachloroanisole 49.75 47.68 48.71 Acenaphthene 20.00 18.63 18.63 α-Benzenehexachloride 1.34 1.34 1.34 Fluorene 40.00 18.63 20.00 Diazinon 2.45 2.45 2.45 Phenanthrene 290.00 180.00 235.00 Lindane 1.64 2.13 1.89 Anthracene 20.00 4.00 10.00 β-Benzenehexachloride 1.76 1.76 1.76 Fluoranthene 780.00 840.00 810.00 Heptachlor 0.12 0.12 0.12 Pyrene 580.00 630.00 605.00 δ-Benzenehexachloride 0.12 0.12 0.12 Benz[a]anthracene 50.00 50.00 50.00 Dacthal 0.88 0.69 0.79 Chrysene 260.00 310.00 285.00 Chlorpyrifos 2.81 2.10 2.46 Benzo[b]fluoranthene 80.00 110.00 95.00 Oxychlordane 1.75 1.75 1.75 Benzo[k]fluoranthene 40.00 30.00 35.00 Heptachlor Epoxide 7.32 8.64 7.98 Benzo[a]pyrene 10.00 10.00 10.00 trans-Chlordane 7.17 8.65 7.91 Indeno[1,2,3-c,d]pyrene 10.00 10.00 10.00 trans-Nonachlor 5.68 6.84 6.26 Dibenz[a,h]anthracene 4.00 4.00 4.00 o,p’-DDE 0.89 0.89 0.89 Benzo[g,h,i]perylene 20.00 20.00 20.00 Cis-Chlordane 9.63 11.59 10.61 Benzo[b]thiophene 24.57 24.57 24.57 Endosulfan 2.05 3.00 2.53 2-methylnaphthalene 24.63 24.63 24.63 p,p’-DDE 7.99 3.38 5.69 1-methylnaphthalene 10.00 9.18 9.18 Dieldrin 26.05 32.19 29.12 Biphenyl 4.00 4.00 4.00 o,p’-DDD 1.60 1.60 1.60 1-ethylnaphthalene 4.00 4.00 4.00 Endrin 1.75 1.75 1.75 1,2-dimethylnaphthalene 10.00 4.00 5.00 Cis-Nonachlor 1.81 1.93 1.81 4-methylbiphenyl 40.10 40.10 40.10 o,p’-DDT 1.30 1.42 1.30 2,3,5-trimethylnaphthalene 20.00 4.00 10.00 p,p’-DDD 2.08 3.22 2.65 1-methylfluorene 30.00 10.00 20.00 Endosulfan-II 2.52 4.28 3.40 Dibenzothiophene 20.00 10.00 15.00 p,p’-DDT 2.83 4.53 3.27 2-methylphenanthrene 80.00 70.00 75.00 Endosulfan Sulfate 0.70 0.76 0.70 9-methylanthracene 4.00 4.00 4.00 Methoxychlor 0.12 1.06 0.53 3,6-dimethylphenanthrene 40.00 40.00 40.00 Mirex 0.12 0.12 0.12 2-methylfluoranthene 30.00 40.00 35.00 Cis-Permethrin 2.72 1.13 1.40 Benzo[b]naphtho[2,1-d]thiophene 40.00 50.00 45.00 trans-Permethrin 0.42 4.62 2.31 Benzo[e]pyrene 60.00 80.00 70.00 Total PCBs 501.16 316.21 408.69 Perylene 130.00 110.00 120.00 3-methylcholanthrene 4.00 4.00 4.00


72

Table V (continued)


CERC Site # 44, Deployment # 1, Station ID 9-DDD006.61



73

Table V (continued)


CERC Site # 45, Deployment # 1, Station ID 4-ABWA008.53



74

Table V (continued)


CERC Site # 46, Deployment # 1, Station ID 4-AMCG000.56



75

Table V (continued)


CERC Site # 48, Deployment # 1, Station ID 4-ABOR033.22



76

Table V (continued)


CERC Site # 49, Deployment # 1, Station ID 4-AFRY006.08



77

Table V (continued)


CERC Site # 50, Deployment # 1, Station ID 9-WLKO26.82



78

Table V (continued)


CERC Site # 1, Deployment # 2, Station ID 2-RVN022.61



79

Table V (continued)


CERC Site # 2, Deployment # 2, Station ID 2-HAK004.34



80

Table V (continued)


CERC Site # 4, Deployment # 2, Station ID 2-BLB002.04



81

Table V (continued)


CERC Site # 13, Deployment # 2, Station ID 2-BLK001.92



82

Table V (continued)


CERC Site # 14, Deployment # 2, Station ID 4-AHRN007.65

OCPs & PCBs Rep # 1 Rep # 2 Mean PAHs Rep # 1 Rep # 2 Mean

1.10 1.10 1.10 Naphthalene 46.94 46.94 46.94 Trifluralin 4.00 Hexachlorobenzene 1.64 1.29 1.47 Acenaphthylene 4.00 4.00

Pentachloroanisole 22.10 19.00 20.55 Acenaphthene 20.00 20.00 20.00 α-Benzenehexachloride 1.34 1.34 1.34 Fluorene 20.00 20.00 20.00

15.67 2.45 7.83 Phenanthrene 100.00 90.00 95.00 Diazinon Lindane 1.53 1.53 1.53 Anthracene 4.00 4.00 4.00 β-Benzenehexachloride 1.76 1.76 1.76 Fluoranthene 40.00 30.00 35.00 Heptachlor 0.12 0.12 0.12 Pyrene 40.00 30.00 35.00

0.12 0.12 0.12 Benz[a]anthracene 4.00 4.00 4.00 δ-Benzenehexachloride Dacthal 0.36 0.36 0.36 Chrysene 88.45 88.45 88.45 Chlorpyrifos 1.12 1.12 1.12 Benzo[b]fluoranthene 4.00 4.00 4.00 Oxychlordane 1.75 1.75 1.75 Benzo[k]fluoranthene 4.00 4.00 4.00

2.55 2.55 2.55 Benzo[a]pyrene 4.00 4.00 4.00 Heptachlor Epoxide trans-Chlordane 1.81 1.07 1.44 Indeno[1,2,3-c,d]pyrene 4.00 4.00 4.00 trans-Nonachlor 1.25 0.22 0.74 Dibenz[a,h]anthracene 4.00 4.00 4.00 o,p’-DDE 0.89 0.89 0.89 Benzo[g,h,i]perylene 9.18 9.18 9.18 cis-Chlordane 1.66 1.14 1.20 Benzo[b]thiophene 24.57 24.57 24.57

0.55 24.63 24.63 1.31 0.80Endosulfan 2-methylnaphthalene 24.63 p,p’-DDE 2.69 2.47 2.58 1-methylnaphthalene 20.00 20.00 20.00 Dieldrin 1.22 1.22 1.22 Biphenyl 4.00 4.00 4.00 o,p’-DDD 1.60 1.60 1.60 1-ethylnaphthalene 10.00 10.00 10.00 Endrin 1.88 1.75 1.75 1,2-dimethylnaphthalene 4.00 4.00 4.00 cis-Nonachlor 1.81 1.81 1.81 4-methylbiphenyl 40.10 40.10 40.10 o,p’-DDT 1.30 1.30 1.30 2,3,5-trimethylnaphthalene 10.00 10.00 10.00 p,p’-DDD 1.28 1.28 1.28 1-methylfluorene 10.00 10.00 10.00 Endosulfan-II 0.39 0.39 0.39 Dibenzothiophene 10.00 4.00 5.00 p,p’-DDT 2.83 2.83 2.83 2-methylphenanthrene 10.00 10.00 10.00 Endosulfan Sulfate 0.70 0.70 0.70 9-methylanthracene 4.00 4.00 4.00 Methoxychlor 0.12 0.12 0.12 3,6-dimethylphenanthrene 4.00 4.00 4.00 Mirex 0.12 0.12 0.12 2-methylfluoranthene 4.00 4.00 4.00 cis-Permethrin 1.13 1.13 1.13 Benzo[b]naphtho[2,1-d]thiophene 4.00 4.00 4.00 trans-Permethrin 0.42 0.42 0.42 Benzo[e]pyrene 4.00 4.00 4.00 Total PCBs 14.09 14.09 14.09 Perylene 20.00 20.00 20.00 3-methylcholanthrene 4.00 4.00 4.00


83

Table V (continued)


CERC Site # 15, Deployment # 2, Station ID Not Given



84

Table V (continued)


CERC Site # 18, Deployment # 2, Station ID Not Given OCPs & PCBs Rep # 1 Rep # 2 Mean PAHs Rep # 1 Rep # 2 Mean Trifluralin 1.10 1.14 1.10 Naphthalene 46.94 46.94 46.94 Hexachlorobenzene 0.84 0.84 0.84 Acenaphthylene 4.00 4.00 4.00 Pentachloroanisole 8.49 8.38 8.44 Acenaphthene 18.63 18.63 18.63 α-Benzenehexachloride 1.34 1.34 1.34 Fluorene 18.63 18.63 18.63 Diazinon 2.45 4.60 3.33 Phenanthrene 69.87 69.87 69.87 Lindane 1.53 1.53 1.53 Anthracene 4.00 4.00 4.00 β-Benzenehexachloride 1.76 1.76 1.76 Fluoranthene 10.00 4.00 5.00 Heptachlor 0.12 0.12 0.12 Pyrene 10.00 10.00 10.00 δ-Benzenehexachloride 0.12 0.12 0.12 Benz[a]anthracene 4.00 4.00 4.00 Dacthal 0.36 0.36 0.36 Chrysene 88.45 88.45 88.45 Chlorpyrifos 1.12 1.12 1.12 Benzo[b]fluoranthene 4.00 4.00 4.00 Oxychlordane 1.75 1.75 1.75 Benzo[k]fluoranthene 4.00 4.00 4.00 Heptachlor Epoxide 2.55 2.55 2.55 Benzo[a]pyrene 4.00 4.00 4.00 trans-Chlordane 1.29 1.01 1.15 Indeno[1,2,3-c,d]pyrene 4.00 4.00 4.00 trans-Nonachlor 0.31 0.12 0.16 Dibenz[a,h]anthracene 4.00 4.00 4.00 o,p’-DDE 0.89 0.89 0.89 Benzo[g,h,i]perylene 9.18 9.18 9.18 cis-Chlordane 1.14 1.14 1.14 Benzo[b]thiophene 24.57 24.57 24.57 Endosulfan 0.55 0.55 0.55 2-methylnaphthalene 24.63 24.63 24.63 p,p’-DDE 1.71 2.35 1.71 1-methylnaphthalene 10.00 10.00 10.00 Dieldrin 1.22 1.22 1.22 Biphenyl 4.00 4.00 4.00 o,p’-DDD 1.60 1.60 1.60 1-ethylnaphthalene 4.00 4.00 4.00 Endrin 1.75 1.75 1.75 1,2-dimethylnaphthalene 4.00 4.00 4.00 cis-Nonachlor 1.81 1.81 1.81 4-methylbiphenyl 40.10 40.10 40.10 o,p’-DDT 1.38 1.30 1.30 2,3,5-trimethylnaphthalene 4.00 4.00 4.00 p,p’-DDD 1.28 1.28 1.28 1-methylfluorene 10.00 10.00 10.00 Endosulfan-II 0.39 0.39 0.39 Dibenzothiophene 4.00 4.00 4.00 p,p’-DDT 2.83 2.83 2.83 2-methylphenanthrene 4.00 4.00 4.00 Endosulfan Sulfate 0.70 0.85 0.75 9-methylanthracene 4.00 4.00 4.00 Methoxychlor 0.12 0.12 0.12 3,6-dimethylphenanthrene 4.00 4.00 4.00 Mirex 0.12 0.12 0.12 2-methylfluoranthene 4.00 4.00 4.00 cis-Permethrin 1.13 1.13 1.13 Benzo[b]naphtho[2,1-d]thiophene 4.00 4.00 4.00 trans-Permethrin 0.42 0.42 0.42 Benzo[e]pyrene 4.00 4.00 4.00 Total PCBs 14.09 14.09 14.09 Perylene 4.00 4.00 4.00 3-methylcholanthrene 4.00 4.00 4.00


85

Table VI

Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 1, Deployment # 1, Station ID # 6-BCLN290.74

Water Water OCPs & PCBs Concentration PAHs Concentration Trifluralin 15.87 Naphthalene 5275.20 Hexachlorobenzene 11.64 Acenaphthylene 85.32 Pentachloroanisole 28.63 Acenaphthene 314.33 α-Benzenehexachloride 56.40 Fluorene 186.84 Diazinon 403.27 Phenanthrene 1857.96 Lindane 91.61 Anthracene 82.97 β-Benzenehexachloride 74.39 Fluoranthene 1072.35 Heptachlor 1.02 Pyrene 1624.79 δ-Benzenehexachloride 14.92 Benz[a]anthracene 200.35 Dacthal 5.04 Chrysene 767.72 Chlorpyrifos 9.35 Benzo[b]fluoranthene 363.66 Oxychlordane 34.04 Benzo[k]fluoranthene 154.55 Heptachlor Epoxide 46.84 Benzo[a]pyrene 47.92 trans-Chlordane 51.25 Indeno[1,2,3-c,d]pyrene 49.06 trans-Nonachlor 62.68 Dibenz[a,h]anthracene 24.98 o,p’-DDE 4.98 Benzo[g,h,i]perylene 85.86 cis-Chlordane 82.99 Endosulfan N/A p,p’-DDE 5.12 Dieldrin 90.24 o,p’-DDD 79.04 Endrin 12.82 cis-Nonachlor 18.63 o,p’-DDT 6.23 p,p’-DDD 25.49 p,p’-DDT 14.77 Methoxychlor 0.98 Mirex 0.49 Total PCBs 60.50

NOTE: All pg/L water concentration estimates are reported without censoring for significant figures (two significant figures are justified). The "NA" values indicate that no uptake rate constant was available for that analyte. All bolded values represent water concentrations based on SPMD concentration that were >MDL and <MQL. Italicized values represent water concentrations based on SPMD concentrations at the MDL for that analyte.

86

Table VI (continued)

Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 2 Deployment # 1, Station ID 6-CNFH020.93



87


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 3, Deployment # 1, Station ID 6-BPOW133.00



88


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 4, Deployment # 1, Station ID 2-XUD000.15



89


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 5, Deployment # 1, Station ID 9-SNK019.59



90


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 8, Deployment # 1, Station ID 4-ASRE020.75



91


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 9, Deployment # 1, Station ID 6-BPOW141.45



92


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 10, Deployment # 1, Station ID 2-MFK002.21



93


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 12, Deployment # 1, Station ID 6-ADI5013.73



94


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 13, Deployment # 1, Station ID 1-BSTH029.45



95


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 15, Deployment # 1, Station ID 1-AGAN000.32

Water Water OCPs & PCBs Concentration PAHs Concentration Trifluralin 13.15 Naphthalene N/A Hexachlorobenzene 22.28 Acenaphthylene 77.16 Pentachloroanisole 148.84 Acenaphthene 248.93 α-Benzenehexachloride 32.97 Fluorene 158.06 Diazinon 375.22 Phenanthrene 536.43 Lindane 56.82 Anthracene 20.18 β-Benzenehexachloride N/A Fluoranthene 801.29 Heptachlor 1.44 Pyrene 971.18 δ-Benzenehexachloride N/A Benz[a]anthracene 59.82 Dacthal 26.19 Chrysene 952.39 Chlorpyrifos 71.56 Benzo[b]fluoranthene 134.59 Oxychlordane 40.17 Benzo[k]fluoranthene 63.34 Heptachlor Epoxide 17.97 Benzo[a]pyrene 61.53 trans-Chlordane 65.53 Indeno[1,2,3-c,d]pyrene 52.21 trans-Nonachlor 73.16 Dibenz[a,h]anthracene 74.90 o,p’-DDE 11.66 Benzo[g,h,i]perylene 208.04 cis-Chlordane 92.66 Endosulfan 167.58 p,p’-DDE 154.51 Dieldrin 308.20 o,p’-DDD 38.70 Endrin 202.84 cis-Nonachlor 27.77 o,p’-DDT 35.83 p,p’-DDD 64.23 p,p’-DDT 89.46 Methoxychlor 3.45 Mirex 1.10 Total PCBs 126.45


96


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 17, Deployment # 1, Station ID 3-BLK001.92



97


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 18, Deployment # 1, Station ID 2-XUE000.31



98


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 19, Deployment # 1, Station ID 2-JK5070.97



99


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 21, Deployment # 1, Station ID 3-CRC001.38



100


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 22, Deployment # 1, Station ID 2-APP061.07

Water Water OCPs & PCBs Concentration PAHs Concentration Trifluralin 33.42 Naphthalene 4944.54 Hexachlorobenzene 21.45 Acenaphthylene 64.89 Pentachloroanisole 185.26 Acenaphthene 249.88 α-Benzenehexachloride 45.19 Fluorene 399.02 Diazinon 569.95 Phenanthrene 585.64 Lindane 76.46 Anthracene 25.25 β-Benzenehexachloride 68.52 Fluoranthene 712.56 Heptachlor 0.87 Pyrene 455.25 δ-Benzenehexachloride 2.41 Benz[a]anthracene 40.47 Dacthal 3.73 Chrysene 631.64 Chlorpyrifos 23.55 Benzo[b]fluoranthene 107.12 Oxychlordane 26.53 Benzo[k]fluoranthene 36.42 Heptachlor Epoxide 17.66 Benzo[a]pyrene 33.88 trans-Chlordane 32.08 34.69 Indeno[1,2,3-c,d]pyrenetrans-Nonachlor 26.92 Dibenz[a,h]anthracene 44.15 o,p’-DDE 8.80 Benzo[g,h,i]perylene 139.27 cis-Chlordane 35.16 Endosulfan N/A p,p’-DDE 28.82 Dieldrin 17.93 o,p’-DDD 93.15 Endrin 10.05 cis-Nonachlor 21.91 o,p’-DDT 37.42 p,p’-DDD 37.30 p,p’-DDT 21.94 Methoxychlor 15.38 Mirex 0.87 Total PCBs 106.92


101


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 23, Deployment # 1, Station ID 1-BNF5048.74



102


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 24, Deployment # 1, Station ID 8-MPN046.13



103


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 25, Deployment # 1, Station ID 2-BLB002.04



104


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 28, Deployment # 1, Station ID 3-JOA002.68



105


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 29, Deployment # 1, Station ID 1-ACAA000.83



106


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 31, Deployment # 1, Station ID 8-MTA012.09



107


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 32, Deployment # 1, Station ID 5-ASAP004.00



108


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 33, Deployment # 1, Station ID 5-BPCT002.16



109


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 34, Deployment # 1, Station ID 5-ABLC000.88



110


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 35, Deployment # 1, Station ID 5-ANTW097.27



111


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 36, Deployment # 1, Station ID 9-NBS006.58



112


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 37, Deployment # 1, Station ID 5-AMHN097.83



113


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 38, Deployment # 1, Station ID 2-NWD004.15



114


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 40, Deployment # 1, Station ID 9-PLM000.35



115


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 41, Deployment # 1, Station ID 5-AFON024.32



116


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 42, Deployment # 1, Station ID 2-CAT026.55



117


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 43, Deployment # 1, Station ID 3-MTN003.31



118


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 44, Deployment # 1, Station ID 9-DDD006.61



119


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 45, Deployment # 1, Station ID 4-ABWA008.53

Water Water OCPs & PCBs Concentration PAHs Concentration Trifluralin 21.46 Naphthalene 4019.13 Hexachlorobenzene 40.30 Acenaphthylene 200.83 Pentachloroanisole 354.43 Acenaphthene 569.23 α-Benzenehexachloride 31.98 Fluorene 770.13 Diazinon 1492.60 Phenanthrene 2791.01 Lindane 55.55 Anthracene 78.10 β-Benzenehexachloride 54.43 Fluoranthene 5883.15 Heptachlor 1.69 Pyrene 2771.13 δ-Benzenehexachloride 1.77 Benz[a]anthracene 78.10 Dacthal 55.65 Chrysene 1378.28 Chlorpyrifos 23.41 Benzo[b]fluoranthene 413.48 Oxychlordane 51.21 Benzo[k]fluoranthene 175.73 Heptachlor Epoxide 102.35 Benzo[a]pyrene 65.39 trans-Chlordane 89.32 66.94 Indeno[1,2,3-c,d]pyrenetrans-Nonachlor 77.57 Dibenz[a,h]anthracene 85.20 o,p’-DDE 16.97 Benzo[g,h,i]perylene 268.79 cis-Chlordane 173.60 Endosulfan N/A p,p’-DDE 17.46 Dieldrin 236.66 o,p’-DDD 34.12 Endrin 25.13 cis-Nonachlor 42.29 o,p’-DDT 21.25 p,p’-DDD 23.69 p,p’-DDT 35.56 Methoxychlor 0.57 Mirex 1.69 Total PCBs 206.37


120


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 46, Deployment # 1, Station ID 4-AMCG000.56



121


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 48, Deployment # 1, Station ID 4-ABOR033.22



122


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 49, Deployment # 1, Station ID 4-AFRY006.08



123


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 50, Deployment # 1, Station ID 9-WLKO26.82



124


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 1, Deployment # 2, Station ID 2-RVN022.61



125


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 2, Deployment # 2, Station ID 2-HAK004.34



126


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 4, Deployment # 2, Station ID 2-BLB002.04



127


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 13, Deployment # 2, Station ID 2-BLK001.92



128


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 14, Deployment # 2, Station ID 4-AHRN007.65



129


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 15, Deployment # 2, Station ID Not Given



130


Estimated Water Concentrations (pg/L) Derived from SPMD Data CERC Site # 18, Deployment # 2, Station ID Not Given



131

Table VII

Spiked SPMD Recovery Data Mean Recovery Standard

Deviation Mean

Recovery StandardDeviation

OCPs & PCBs % (n = 7) PAHs % (n = 5) Trifluralin 50.8 43.0 Naphthalene 39.4 22.5 Hexachlorobenzene 77.6 10.0 Acenaphthylene 52.2 23.4 Pentachloroanisole 86.3 10.2 Acenaphthene 56.3 21.0 α-Benzenehexachloride 65.9 9.0 Fluorene 63.7 11.1 Diazinon 22.6 19.6 Phenanthrene 75.7 5.3 Lindane 80.1 11.9 Anthracene 71.8 4.2 β-Benzenehexachloride 70.9 11.5 Fluoranthene 81.9 4.1 Heptachlor 62.0 26.5 Pyrene 82.6 4.1 δ-Benzenehexachloride 64.4 17.4 Benz[a]anthracene 82.0 3.9 Dacthal 24.5 7.7 Chrysene 84.9 3.9 Chlorpyrifos 35.5 27.2 Benzo[b]fluoranthene 82.1 4.7 Oxychlordane 82.3 30.7 Benzo[k]fluoranthene 84.1 3.6 Heptachlor Epoxide 75.2 14.4 Benzo[a]pyrene 78.2 4.3 trans-Chlordane 73.7 12.0 Indeno[1,2,3-c,d]pyrene 80.8 4.8 trans-Nonachlor 60.3 7.6 Dibenz[a,h]anthracene 82.7 6.9 o,p’-DDE 109 106 Benzo[g,h,i]perylene 81.7 5.9 cis-Chlordane 87.2 41.2 Endosulfan 73.9 13.9 p,p’-DDE 129 88.3 Dieldrin 74.5 11.8 o,p’-DDD 94.9 40.5 Endrin 91.0 30.5 cis-Nonachlor 57.7 11.8 o,p’-DDT 82.3 12.4 p,p’-DDD 75.0 13.1 Endosulfan-II 82.5 18.1 p,p’-DDT 103 31.6 Endosulfan Sulfate 64.1 14.3 Methoxychlor 50.6 13.5 Mirex 78.3 13.5 cis-Permethrin 25.6 42.5 trans-Permethrin 29.8 38.9 Total PCBs 83.5 12.4

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Table VIII

Site Specific keP Values Derived from the Analysis of

SPMDs for Residual PRC Levels (keP values with an asterisk are based on pyrene-d10, values without asterisk represent phenanthrene-d10)

CERC Site # Dep # Station ID keP CERC Site# Dep # Station ID keP

Site # 1 # 1 6-BCLN290.74 0.0364* Site # 33 # 1 5-BPCT002.16 0.0315 Site # 2 # 1 6-CNFH020.93 0.0272* Site # 34 # 1 5-ABLC000.88 0.0390 Site # 3 # 1 6-BPOW133.00 0.0169* Site # 35 # 1 5-ANTW097.27 0.0263 Site # 4 # 1 2-XUD000.15 0.0282 Site # 36 # 1 9-NBS006.58 0.0552 Site # 5 # 1 9-SNK019.59 0.0504* Site # 37 # 1 5-AMHN097.83 0.0053* Site # 8 # 1 4-ASRE020.75 0.0048* Site # 38 # 1 2-NWD004.15 0.0473 Site # 9 # 1 6-BPOW141.45 0.0172* Site # 40 # 1 9-PLM000.35 0.0340 Site # 10 # 1 2-MFK002.21 0.0121* Site # 41 # 1 5-AFON024.32 0.0134* Site # 12 # 1 6-ADI5013.73 0.0117* Site # 42 # 1 2-CAT026.55 0.0134 Site # 13 # 1 1-BSTH029.45 0.0421* Site # 43 # 1 3-MTN003.31 0.0139* Site # 15 # 1 1-AGAN000.32 0.0168* Site # 44 # 1 9-DDD006.61 0.0126* Site # 17 # 1 3-BLK001.92 0.0184 Site # 45 # 1 4-ABWA008.53 0.0107* Site # 18 # 1 2-XUE000.31 0.0053 Site # 46 # 1 4-AMCG000.56 0.0257* Site # 19 # 1 2-JK5070.97 0.0403 Site # 48 # 1 4-ABOR033.22 0.0162* Site # 21 # 1 3-CRC001.38 0.0364 Site # 49 # 1 4-AFRY006.08 0.0173 Site # 22 # 1 2-APP061.07 0.0113* Site # 50 # 1 9-WLKO26.82 0.0188* Site # 23 # 1 1-BNF5048.74 0.0427 Site # 1 # 2 2-RVN022.61 0.0275 Site # 24 # 1 8-MPN046.13 0.0437* Site # 2 # 2 2-HAK004.34 0.0210 Site # 25 # 1 2-BLB002.04 0.0351 Site # 4 # 2 2-BLB002.04 0.0474 Site # 28 # 1 3-JOA002.68 0.0167* Site # 13 # 2 2-BLK001.92 0.0191 Site # 29 # 1 1-ACAA000.83 0.0284 Site # 14 # 2 4-AHRN007.65 0.0283 Site # 31 # 1 8-MTA012.09 0.0199* Site # 15 # 2 Not Given 0.0539 Site # 32 # 1 5-ASAP004.00 0.0192* Site # 18 # 2 Not Given 0.0136

133

Figure I

SPMD Analytical Scheme

PAH Fraction PCB/OC Fraction

SPMD Samples

Post-Dialysis Sample (Composite of Replicates)

GC-MSD Analysis

PCB Fraction GC-ECD Analysis

OC Fraction GC-ECD Analysis

SEC with Chemical Class Appropriate Collect Window

Gravity Column Cleanup (TriAdsorbent Cleanup)

SEC with Chemical Class Appropriate Collect Window

Gravity Column Cleanup (Florisil)

Gravity Column Cleanup/Fractionation (Silica Gel)

Dialytic Extraction

ple Split (50:50) Sam

134

Figure 2

Distribution of PCA in Samples (ng/SPMD) Across Sites

0

50

100

150

200

250

300

350

400

450

1 3 5 9 12 15 18 21 23 25 29 32 34 36 38 41 43 45 48 50 2 13 15

CERC Site ID

Deployment # 1 Deployment # 2

ng P

CA

/SPM

D

135

Use of SPMD Technology for a Probabilistic Assessment - USGS

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